Hybrid heterogeneous solid acid catalysts polyoxometalate-decorated metal organic framework (POM@MOFs) thin films were synthesized from POMs and metal hydroxide nanostrands via a self-confinement method at room temperature, which show high hydrolyzing activity (1027.5 μmol g-1 min-1) for ethyl acetate with durable stability and an easy recovery. This provides a general way to easily prepare nano POM@MOF thin film catalysts.