Nps-Cu/TiO2 composite films with different sputtering time and layer numbers of Cu were prepared by alternate magnetron sputtering. The XRD and TEM results confirm the formation of approximately spherical Cu nanoparticles embedded in TiO2 matrix. The optical absorption peaks assigned to the surface plasmon resonance (SPR) of Cu nanoparticles were observed in the wavelength range of 600–900 nm. The SPR peaks show enhanced intensity and red-shift due to increasing Cu Nps size and decreasing space between them with increased sputtering time of Cu. The Nps-Cu/TiO2 composite film with one bottom layer of Cu nanoparticles and one embedded within the TiO2 film has proven to achieve the highest enhanced photocatalytic efficiency compared with the pure TiO2 film, which is elucidated with the photogenerated carriers separation mechanism related with the embedded Cu nanoparticles.