Pique, 25, has already established himself as one of the world's outstanding centre-backs. But there is a worry among Spain fans, with Pique coming into Euro 2012 on the back of one of the most disappointing campaigns of his career.
He started just 17 league games for Barcelona, as injuries and suspension took their toll and saw him fall behind Puyol and Javier Mascherano in the pecking order.
For Barca coach Pep Guardiola, it wasn't just about Pique's on-pitch issues but his time spent with pop star girlfriend Shakira.
Thanks to his much-publicised relationship with the Colombian singer, Pique is as much a feature of gossip magazines as Spain's sporting press and many believe his high-profile private life has had an adverse effect on his on-pitch form.
Rather than the "waka waka" -- Shakira's official anthem for the 2010 World Cup -- critics say Pique should be focusing more on the "tiki-taka", the short-pass and move style that has brought so much success to Barcelona and Spain.
Pique has formed a formidable partnership with Puyol for club and country in recent years.
Now, with Puyol recovering from a knee injury, Pique's partner in Vicente Del Bosque's side at the Euros will be Real Madrid's Sergio Ramos.
Ramos is a year younger than Pique but is far more experienced at international level and played twice as many games in La Liga in 2011/12.
"I have had a difficult season," Pique told Catalan television recently, although he maintained there was never any problem between him and Guardiola.
"A lot of things have been exaggerated. Pep and I have always had a fluid relationship. No conflict has ever come between us."
When he is on his game, Pique is a class act. His use of the ball is better than almost any other centre-back in the world today and has earned him the nickname "Piquenbauer" in a nod to the great German sweeper Franz Beckenbauer.
"I have to learn more things to arrive to his level. He's one of the best players in history. So when they say 'Piquenbauer' I think it's too much," Pique said in an interview with Sports Illustrated last year.
Pique speaks eloquently -- and is not afraid to speak his mind, even if it upsets those in authority.
This season he has accused Real Madrid coach Jose Mourinho of "destroying Spanish football" and claimed a referee's decision to send him off in a league game was "premeditated".
There are few others in football like Pique. He is the son of a well-to-do Catalan family, whose father was a doctor and whose grandfather -- ironically named Amador Bernabeu like the home of Barca rivals Real Madrid -- was a Barcelona director.
Pique began his career at La Masia, Barca's famed youth academy, but was coaxed away to England at a young age, joining Manchester United before he had graduated to full professional terms at the Camp Nou.
He featured occasionally for United in 2007-08 as Sir Alex Ferguson's side won the Champions League and the Premier League titles.
Pique could have stayed at Old Trafford and imposed himself there. He had the intelligence and the ability. But instead he decided the time was right to return home, and joined Barcelona for £5 million.
Looking back, that fee appears scandalously low, for Pique quickly became one of the most important players of the Guardiola era.
He was also outstanding in Spain's 2010 World Cup success and very unlucky not to be considered for that year's Ballon d'Or prize.
Del Bosque will be counting on Pique to rediscover that form in Poland and Ukraine as La Roja go looking for yet more glory.