A simple approach to prepare arrays of Au/TiO2 composite nanoparticles by using Au-loaded block copolymers as templates combined with a sol-gel process is described. The organic-inorganic hybrid films with closely packed inorganic nanodomains in organic matrix are produced by spin coating the mixtures of polystyrene-block-poly(ethylene oxide) (PS-b-PEO)/HAuCl4 solution and sol-gel precursor solution. After removal of the organic matrix with deep UV irradiation, arrays of Au/TiO2 composite nanoparticles with different compositions or particle sizes can be easily produced. Different photoluminescence (PL) emission spectra from an organic-inorganic hybrid film and arrays of Au/TiO2 composite nanoparticles indicate that TiO2 and Au components exist as separate state in the initial hybrid film and form composite nanoparticles after the removal of the block copolymer matrix.