∵A∩B={2,5},∴5∈A,A={2,4,5}.
由已知可得a3-2a2-a+7=5.
∴a3-2a2-a+2=0.∴(a2-1)(a-2)=0.∴a=2或a=±1.
(1)當a=2時,B={-4,5,2,25},A∩B={2,5}與題設相符;
(2)當a=1時,B={-4,4,1,12},A∩B={4}與題設矛盾;
(3)當a=-1時,B={-4,2,5,4},A∩B={2,4,5}與題設矛盾.
綜上(1)(2)(3)知a=2,且A∪B={2,4,5}∪{-4,5,2,25}={-4,2,4,5,25}.