According to Mourinho, England will reach the quarter-finals before being beaten by Brazil.
The former Chelsea manager believes Argentina can beat Spain for a place in the quarter-finals.
The 55-year-old is also confident the Germans are set for a significant run, tipping them to beat Belgium in the last-16 round.
The Portuguese gaffer, was clearly impressed with his picks for the final four this summer, saying: “Wow… look at this, two South Americans, the big rivals, Brazil and Argentina. The European champion (Portugal) and the big Germany. That’s incredible!”.