Puyol ended his playing career this summer to take on a backroom role with the Catalan giants, and left his shirt vacant after having worn it since taking the number from Abelardo Fernandez in 2002.
The former centre-back, 36, personally asked for Busquets – who has worn No.16 for much of his first-team career at Barca – to be given his shirt, something the midfielder has admitted he was “thrilled” about.
“I talked to him [Puyol] and he intended to give me the number [five shirt after retiring]. I was thrilled and I did not hesitate for a second,” Busquets told a press conference ahead of Barcelona’s pre-season friendly against HJK Helsinki in Finland.
"I am very happy, it's something that has come through the confidence of my peers,” he said.
“I've learned a lot from Puyol and [Victor] Valdes. Being captain means being aware of everything, being a good partner, but above all, being natural and being yourself,” he added.
The holding midfielder was also asked about the potential arrival of Arsenal centre-back Thomas Vermaelen to the club this summer but Busquets refused to speak about “something that is not confirmed".
Barcelona will take on HJK Helsinki on Saturday before playing Leon FC in their final pre-season friendly ahead of the 2014/15 La Liga season, which kicks off on 23 August.