During the 2020–21 Billie Jean King Cup, Samsonova led the Russian team to their first triumph since 2008, winning all five of her matches in both singles and doubles.

[14] Her biggest achievements were winning consecutive ITF Junior Circuit Grade-2 tournaments in 2016, defeating notable players such as Kaja Juvan and Marta Kostyuk.

[15] In 2013, Samsonova made her professional debut at consecutive ITF Circuit tournaments in Umag, but lost her both singles qualifying matches.

[16][note 1] 2014 saw Samsonova winning her first ITF title at a $10k event in Rome, beating three seeded players to clinch the victory despite being unranked.

Overriding her personal best results, the Russian won her first $25k title at the Open Castilla y León, stunning third seed Başak Eraydın in the final with the loss of just two games.

After a five-match losing streak to start the clay-court season, Samsonova stunned several higher-ranked players, including tenth seed Marie Bouzková, to qualify for the main draw at the French Open on her first attempt.

[24][25] Reaching her second WTA Tour main draw at the rain-plagued Nottingham Open, Samsonova continued her good run of form before falling to former top-15 player Yanina Wickmayer in the final round of qualifying at the Wimbledon Championships, on her debut.

Samsonova received her first direct entry into a WTA Tour main draw at the Ladies Open Lausanne, but lost to lucky loser Han Xinyun in the second round.

In the following week, despite losing to Amandine Hesse in the final qualifying round of the Palermo Ladies Open, she received an entry into the main draw by virtue of an emptied lucky-loser spot.

There, she stunned fourth seed and 56th-ranked Tamara Zidanšek, in straight sets,[26] before hitting 41 winners to beat Lausanne champion Fiona Ferro in the quarterfinals to make her first tour semifinal.

[28] Her good run continued at the WTA 125 Open de Limoges, where she reached the quarterfinals by beating top-100 players Camila Giorgi and Alizé Cornet.

[29][30] She ended the year with a 32–27 win–loss record with an impressive nine top-100 wins, partly due to competing in more WTA Tour tournaments and facing tougher draws in the process.

Starting the year at the Premier-level Brisbane International, Samsonova survived the qualifying rounds which included a straight-sets win over Kristina Mladenovic.

[34] Drawing former French Open champion, Jeļena Ostapenko, in the first round, she was outpowered and committed 24 unforced errors en route a straight-sets defeat.

[36] Heading back to Russia for the St. Petersburg Ladies' Trophy, she qualified for the main draw but fell to fellow Russian Anastasia Potapova in the first round.

[37] Similar to 2019, Samsonova failed to qualify for the main draw at the Qatar Ladies Open and the Dubai Tennis Championships before the COVID-19 pandemic forced the tour to go on a hiatus for a couple of months.

Defeating Kirsten Flipkens in the first round,[38] and exacting revenge for her two losses to the Belgian in 2019, Samsonova set up an interesting clash with top seed Petra Martić.

[45] She ended her trip in Australia with another successful qualifying campaign at the Adelaide International, reaching the main draw and challenging sixth seed Martić to three sets.

[51] Beginning her first career grass-court season at the German Open in Berlin, starting as a qualifier, she reached her first WTA Tour final.

Her campaign began with a tight win over Ana Konjuh in a final-set tiebreak to qualify for the main draw, before stunning Markéta Vondroušová in the first round.

Samsonova then reached her first WTA 500 quarterfinal with a straight-sets defeat of compatriot Veronika Kudermetova, not facing a break point throughout the encounter.

[52] Samsonova prevailed 7–6, 2–6, 7–6 over former top-10 player Madison Keys, saving 8/11 break points in the match,[53] and followed it up with a bigger upset over two-time Grand Slam champion Victoria Azarenka in the semifinal.

She ended season at the BJK Cup Finals, making her debut in the tournament but played a pivotal role in clinching the title for Russia as she went unbeaten throughout the week.

[85] At the US Open, she reached the fourth round for the first time at this major defeating qualifier Sara Bejlek, 14th seed Leylah Fernandez, and Aleksandra Krunić.

[86] In the fourth round, she lost to Ajla Tomljanović after an intense one hour first-set battle, losing eight set points and a 20 minute game.

[87] In Tokyo, she defeated Elena Rybakina, Wang Xinyu,[88] third seed Garbiñe Muguruza,[89] and Zhang Shuai to reached her third final of the season.

Samsonova reached the semifinals at the Adelaide International, defeating qualifiers Marie Bouzková[104] and Belinda Bencic,[105] then second seed Emma Navarro, [106] before losing to eventual champion Madison Keys.

[109] Samsonova has competed for the Russian team since 2021, securing her first nomination at the 2020–21 Billie Jean King Cup Finals where she was the fifth-ranked singles player for Russia.

[74] Continuing her partnership with Kudermetova, they defeated Clara Burel and Alizé Cornet in 47 minutes to seal a 2–1 win over France, booking their spot in the semifinals.

[72] In the final, Samsonova continued her unbeaten run, coming in as a late replacement for an injured Pavlyuchenkova to stun Belinda Bencic, once again from a set down, to clinch the title for Russia.