1. Lionel Messi

It must appear odd to place a player who has scored a brace over other who have scored four goals and hat-tricks. There's good reason for that.
Such was Barcelona's dominance that Madrid went on €500 million spending spree, bringing in Kaka, Cristiano Ronaldo, Karim Benzema among others while Florentino Perez was re-elected. Watching Mourinho's Inter thwart the Catalans in the Champions League in 2010, Perez saw Mourinho as the perfect man to bring an end to this Barcelona behemoth.
Humiliated 5-0 at Camp Nou, the Portuguese shored up his ranks and earned a 1-1 draw in the league game at home. The rivals would go on to face three more times in the same season.
Valencia's Mestalla stadium hosted the Copa del Rey final as Ronaldo's header won Real Madrid the trophy in extra-time. It was seen as the beginning of the end of Barcelona's reign and vindication of hiring Mourinho. The Portuguese's mind games had taken a toll as there was so much animosity brewing, leading to factions in the Spanish national team.
It served as an appetising warm-up for the Champions League semi-final to come, their first European meeting since 2002. The momentum was with Madrid because of the cup win. Guardiola exploded in the presser before the game and is said to have generated a roaring applause from the Barça camp. The stage was set.
Lionel Messi took the game by the scruff of its neck and delivered one of the all-time great performances under pressure, at the Bernabéu no less. Ibrahim Afellay set up the first goal with a low cross from the right as Messi beat Casillas at the near post. The second goal was simpler and far more spectacular. He played a one-two with Busquets who rolled the ball in his path and Messi, with his burst of acceleration and wonderful dribbling, took it past four Real Madrid players to slot it past Casillas with his right foot from an awkward position with little balance. It was an extraordinary goal at a key moment in such a mammoth clash.

It was a psychological blow as that Madrid side was on the up. A second-leg draw at Camp Nou put Barça in the final where they beat United to win their second Champions League title in 3 years.
It's no surprise that this is ranked as one of Messi's most important performances, if not one of his best ever.