In 2009, then manager Slaven Bilić made him the captain of the national team, a position he would hold until his retirement from international football in 2016; the captaincy then passed to Luka Modrić.

After the 2006 FIFA World Cup, Benfica were reported to be after the player's signature but nothing materialized, with what many considered a fallen or rejected sale.

The following season, Shakhtar were trumped to the Premier League title by Dynamo Kyiv as they failed to achieve any silverware.

[28] On 28 August, he played in Shakhtar's 1–0 extra time loss to Barcelona in the 2009 UEFA Super Cup, picking up a yellow card on 65 minutes.

[30] He scored a goal and picked up a yellow card in a 2–0 Ukrainian Cup victory over Dynamo Kyiv on 28 October.

[41] Srna was named in the UEFA Champions League Team of the Year according to player rater (statistics) in the 2010–11 season where Shakhtar lost in the quarter-final to Barcelona.

[46] On 6 May, he played in the Ukrainian Cup Final against Metalurh Donetsk in which Shakhtar emerged victorious after an extra time winner from Oleksandr Kucher made it 2–1.

Darijo began the 2012–13 season with an assist for Luiz Adriano in the sixth-minute of Shakhtar's 2–0 Super Cup victory over Metalurh Donetsk.

[59] On 13 February 2013, Srna netted with an expertly-struck free-kick in the 31st minute in the first leg of the Champions League Round of 16 tie with Borussia Dortmund, which ended in a 2–2 draw.

[67] On 22 June 2018 Srna, signed one-year deal with Italian side Cagliari Calcio with an option to extend it for another year.

Srna made his full international debut for the Croatia national team in a friendly match against Romania in November 2002.

He made a total of six appearances in Croatia's qualifying campaign for Euro 2004, including both play-off matches against Slovenia.

At the Euro 2004 finals, he appeared as a substitute in Croatia's group matches against Switzerland and England, before they were knocked out of the tournament in the first round.

During the 2006 World Cup qualifying, he scored both goals in Croatia's two 1–0 wins over Sweden, including a long-range free kick in the away fixture in Gothenburg.

He was highly praised and remembered for his spectacular 30-yard free kick which put Croatia ahead against Australia in the infamous "Graham Poll three-yellow card" blunder match that ended 2–2.

In September 2006, Srna was temporarily dropped from the Croatian squad for a Euro 2008 qualifying match with Russia because of a late night partying spree in a local disco, along with teammates Boško Balaban and Ivica Olić.

[71] In the 88th minute, he provided a cross which found teammate Eduardo, and allowed him to score and snatch a late win for Croatia.

Srna went on to miss a penalty against Estonia, however his overall contribution to teamwork attack compensated for this mistake, which Croatia quickly capitalised on to win 2–0.

On 12 June, Srna scored the opening goal in the 24th minute of Croatia's 2–1 victory over Germany in their second game of Group B.

At the conclusion of the match, Srna was seen struggling to hold back an emotional breakdown because of Croatia's strong efforts but eventual defeat.

[72][73] Srna started in all three games of the 2012 tournament as the captain, where Croatia finished third behind Spain and Italy, failing to qualify to the next stage.

[74] Croatia qualified for the 2014 World Cup, where Srna served as team captain for his second official international tournament, after Euro 2012.

At Euro 2016 in France, Srna, once again as team captain, played in Croatia's first group stage match against Turkey.

[76] Croatia reached the knock-out phase of the tournament, but lost 1–0 to Portugal through an extra-time Ricardo Quaresma goal.

[78] Srna was born in Metković[79] on Adriatic coast of southern Dalmatia to Bosniak father Uzeir and Croat mother Milka.

[72] While at Shakhtar, Srna frequently bought match tickets for orphans and often financed their travel to the stadium at his own expense.

[72][84][85] In late 2014, he purchased 20 tonnes of tangerines from farms near Metković and had them donated to over 23,000 primary school children in the Donbas region during the ongoing war there.

[86] Srna married long-time girlfriend Mirela Forić, whom he met through mutual friend and footballer Boško Balaban.