A metal-organic framework (MOF) is one kind of crystalline microporous material and is increasingly used as a host of catalytically active guests. Nanostructured materials supported on MOFs have presented enhanced catalytic activity and stability. Templates or several steps are essential to the synthesis of MOF composites. Simple and effective MOF synthesis methods are still challenging. Nanosized copper oxide particles in MOF composites, described as nanosized CuO@HKUST-1, were prepared by a facile solvent-free reaction. These series of CuO@HKUST-1 composites exhibited excellent photocatalytic activity for production of hydrogen and methylene blue (MB) degradation under visible light. This synthesis method provides an effective way to fabricate MOF-related nanocomposite catalysts.