[6] At the end of the campaign, after the team lost a considerable advantage on the table to be finally surpassed by Valencia, Barcelona and Deportivo de La Coruña, the pair was sacked,[7] and the latter returned to his assistant position in Manchester United.

After collecting three losses and two draws in his first nine games in charge, the side eventually finished in third place with 61 points, four behind champions Benfica;[8] additionally, he coached the team to a runner-up run in the UEFA Cup after disposing of the likes of Feyenoord, Middlesbrough and Newcastle United.

His debut took place on 28 March, and it ended with a 2–1 away win over Iran which was the former's first ever victory in that country and the latter's first loss in nearly 40 home games;[20] eventually, the nation failed to reach the finals in South Africa after losing to Bahrain on the away goals rule,[21] and on 10 January 2011 he was relieved of his duties following a 2–1 defeat against Syria in the 2011 AFC Asian Cup opener.

[23] His first major signing was Portuguese international Rúben Micael,[24] and he qualified the club for the group stage of the Champions League for the second time in its history, after disposing of Udinese on penalties.

[25][26] At the end of the campaign, in spite of winning the Taça da Liga and ranking fourth in the league, Braga and Peseiro reached an agreement to terminate the manager's contract.

[30] Even though the third position they occupied at the time of the Spaniard's dismissal was still secured, he collected more losses than his predecessor,[31] and also lost the final of the Taça de Portugal to his former team Braga, on penalties.

[37] In July 2018, Peseiro returned to Sporting after 13 years away, assuming the reins at a club that had lost several key players following fan violence, and whose previous manager Siniša Mihajlović lasted just nine days in the job.

[41] At the 2021 Copa América in Brazil, Venezuela was eliminated from the group stage with two draws and two defeats; Peseiro was praised by pundit Tim Vickery for achieving those results, despite a spate of COVID-19 infections and virus-related travel restrictions that kept key forward Salomón Rondón in China.

[47] He finished runner-up in the 2023 Africa Cup of Nations, losing 2–1 to hosts Ivory Coast;[48] subsequently, he was awarded the Order of the Niger by president Bola Tinubu.