In an interview with RT Sport, Mourinho named Portugal, Brazil, Argentina and Germany as his World Cup semi-finalists.
The United boss is backing his native Portugal for a productive run in Russia and believes they can beat Uruguay and France to reach the last-eight.
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.