The visitors named an impressive team including Spain internationals Santi Cazorla, Bruno and Borja Valero and experienced midfielder Marcos Senna.
In an even first half at Pittodrie, both sides drew good saves from Aberdeen's on-loan goalkeeper David Gonzalez and Diego Lopez in the Villarreal goal.
The deadlock was broken in the 53rd minute through half-time substitute Giuseppe Rossi, with the Italy international coolly slotting home from 12 yards.
A crowd of 10,000 showed up for Mackie's big night and he nearly capped it in style but his 73rd minute effort sneaked inches wide.
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