[en] Highlights: • Electronic structure of Cu-doped anatase TiO2 (101) surface has been studied by DFT. • Cu-doped (101) surface exhibits a blue shift in optical absorption spectra. • Cu-doped (101) surface forms a wide absorption band at wavelength around 400 nm. Structure and physical properties of anatase TiO₂ (101) surface doped with copper have been studied by using density functional theory. Results show that [email protected] and [email protected] systems behave as p and n type semiconductors, respectively. Anatase TiO₂ (101) surface exhibits a blue shift in optical absorption spectra compared with pure TiO₂ bulk materials. Enhanced photocatalytic activity at wavelength around 400 nm could be contributed by the change in electronic structure.