[2][3][4] Zambrano joined Bundesliga club Schalke 04 at the age of 16 after playing in the U-17 World Cup in 2005, with Peru as hosts.

"[8] Zambrano has been compared with Brazilian defender Lúcio for his style of play and great defense, offense, and speed.

[9][10] Zambrano immediately became a cornerstone in defence and an undisputed starter for the U-19 team and scored a large number of goals.

[14] In the 2009–10 season, Zambrano finally got a big breakthrough when he made his Schalke 04’s first team debut, starting the whole game and scored his first goal, in a 4–0 win against Germania Windeck in the first round of the DFB Pokal.

[25] Zambrano played a role when he set up a goal for Gerald Asamoah to score the equaliser, as FC St. Pauli won 2–1 against Borussia Mönchengladbach on 21 September 2010.

[30] Although the club was eventually relegated since being sidelined, Zambrano finished his first season, making twenty–one appearances and scoring once in all competitions.

[34] It was not until on 4 February 2012 when he made his return to the first team, starting a match and played 45 minutes before being substituted at half time, in a 2–1 loss against Alemannia Aachen.

[43] He made a good start to the team by helping the side reach at the top of the table after winning the first four league matches of the season.

[48] During a 3–1 win against Fortuna Düsseldorf on 4 May 2013, Zambrano was caught on camera when he is suspected of having deliberately kicked his opponent Stelios Malezas against his right leg in the 57th minute.

Ahead of the 2013–14 season, Zambrano was linked to La Liga side Sevilla but the club responded that they do not wish to sell him.

[53] Zambrano played in both legs of the UEFA Europa League Play–Offs against Qarabağ, helping the side win 4–1 to qualify the Group Stage.

[55] A month later on 3 October 2013, Zambrano set up the club's third goal of the game, in a 3–0 win against APOEL in a UEFA Europa League Group Stage match.

[58] During a 1–0 loss against Borussia Dortmund in the quarter–finals of the DFB Pokal on 11 February 2014, he found himself in clashing with Robert Lewandowski throughout the match.

[76] Amid the transfer speculation, he made his return to the starting line–up, playing 90 minutes, in a 3–2 win against VfL Wolfsburg on 24 January 2016.

On 3 July 2016, Zambrano moved to Russia, signing with FC Rubin Kazan, for an estimated fee of €3 million.

[84] After serving a one match suspension, Zambrano made his return, starting the whole game, in a 3–2 win against FC Ufa on 5 November 2016.

[90] Zambrano made his PAOK debut on 20 September 2017, starting the whole game, in a 2–1 win against Levadiakos in the Kypello Elladas.

[91] Four days later on 24 September 2017, he made his league debut for the club, starting the whole game once again, in a 1–0 win against PAS Giannina.

[101][102] Because of his lack of prominence in Switzerland and negligence from the Ukrainian giant, it was announced on 31 January 2020 that he agreed to leave the club.

[107] Zambrano made his Boca Juniors debut on 4 March 2020, where he started and played 66 minutes before being substituted, in a 1–1 draw against Caracas.

[108] Four days later on 8 March 2020, Zambrano made his league debut for the club, again starting and played 68 minutes before being substituted, in a 1–0 win against Gimnasia LP, resulting Boca Juniors becoming champions.

[110] Zambrano rescinded his contract with Boca Juniors in December 2022, after arguing with coach Hugo Ibarra, who had previously separated him from the senior squad due to acts of indiscipline.

[112] Prior to his appointment at Alianza Lima, he stated in an interview that he had been previously offered from clubs in Uruguay, Brazil and the United States but declined them due to wanting Alianza Lima to win their third championship title in a row at the Peruvian Primera División as well as the club's participation in the 2023 Copa Libertadores.

On 26 March 2008, Zambrano made his senior international debut for the Peru national team in a friendly match against Costa Rica.

[117] Zambrano was chosen to participate in the 2011 Copa América, but an injury suffered against Senegal in a friendly game, days before the tournament began, kept him out.

[126] Seven months later on 1 April 2015, Zambrano captained the national side for the first time in his career, as Peru lost 1–0 against Venezuela.

"[135] In May 2019, Zambrano was named in Peru's final 23-man squad for the 2019 Copa América by manager Ricardo Gareca, earning his first call–up in three years.

[137] Despite suffering from an injury, Zambrano became the national side first choice centre–back position and helped Peru reach the final of the Copa América.

[139] Growing up in Callao, Peru, Zambrano revealed his childhood, saying: "As a child, I was always on the street, playing with friends with a glass ball.

When I come to Peru, I visit my friends — we no longer live in that dangerous area, but in a more peaceful place — we often play this game.