The Blues handed their premiership competitors a 3-1 defeat to set up a semi-final clash with Asante Kotoko on July 10 at the Accra Sports Stadium.
Godfred Gyasi opened the scoring just before the half hour mark for All Stars before Major Baah Tetteh doubled their seven minutes later.
Siedu Zeeda put the game beyond Medeama when he struck the third goal only for Zakaria Atia to get a consolation for the visitors.
Second-tier side, Nania FC are already in the final as they would await the winner of the Kotoko and All Stars clash.
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