We have succeeded to prepare Au nanopareticle deposited TiO2 photocatalysts (Au/TiO2) with control of Au nanoparticle size to be around 8 nm and variation of number density using a colloid photodepostion method. The prepared Au/TiO2 exhibits activity on decomposition (oxidation) of formic acid by thermally activated and photo-activated catalytic reactions. The thermally activated catalytic decomposition gradually increases with increasing the number density of deposited Au NPs and saturated, suggesting that the decomposition occurs on Au NPs surface and/or near the interface of TiO2 and Au NPs. On the other hand, the photocatalytic decomposition is significantly improved with rather small number density deposition of Au NPs and disappeared with high number density deposition. ESR measurements of Au/TiO2 in the surrounding similar to the photocatalytic decomposition suggests that electrons excited by plasmon resonance absorption in the Au NPs transfer to TiO2 to promote the decomposition. However, high number density deposition enhances electron capture by neighboring Au NPs and reduces the photocatalytic activity. Thus there should be the optimum number density of Au NPs on TiO2 for photocatalytic decomposition of formic acid.