Mourinho said that since Spain have dominated football in the last four to six years other teams have learned how to play against them, but the world champions themselves were unable to adapt in response.
"I think it is fair to say that there is a big responsibility [for Spain's failure] in Holland and Chile," he told Eurosport. "They did what I think in modern football you have to do - you have to be strategic.
"People learn how to play against the best teams and when the best teams play always believing that their philosophy is the one, the other people learn.
"Spain was so amazing in the past four, six years - they were so amazing in the way that they were playing football - that people learn, people look, people study."
Holland and Spain have qualified from Group B, while Australia join Spain in their early exit.