The Barcelona star has come under regular fire for his performances on the field and his support off the pitch for his pro-Catalan stance.
Pique, who played in the Spain team which won the 2010 World Cup and 2012 European championships, was criticised in the Spanish media following Sunday's 2-0 World Cup qualifying win against Albania, for allegedly removing the national colours from his playing strip.
The accusations were the last straw for the defender who has played 85 times for his country.
"The World Cup in Russia is going to be my last tournament with the national team and I hope to take a lot of pleasure from these last two years," he said after Sunday's match.
"This is not a decision that I have taken today, I have been thinking about it. But the criticisms today have added to what has happened over the last few years."
Spanish media outlets said Pique had cut short the sleeves of his team unform to remove the national flag colours of red and yellow.
The Spanish Football Federation sprang to his defence, pointing out that the Spanish colours did not feature on the team strip worn in Albania.
A federation statement said the national colours: "only appear on the short-sleeved version of the team strip and not on the long-sleeved model worn by Pique."
The wealthy Catalan region has been calling for more autonomy in recent years from Madrid and regional lawmakers last month approved a plan to call a referendum next year on independence.
First capped in 2009, Pique is an automatic choice in central defence for Spain and a key part of their plans for the Moscow World Cup finals, when he will be 31. But some fans angered by his support for independence from Spain, say he should he be dropped.
"There are also people who believe that it's better that I am not here," said Pique.