Recently, Cu₂(OH)PO₄ was found as the first photocatalyst active in the near-infrared(NIR) region of the solar spectrum (Angew. Chem., Int. Ed., 2013, 52, 4810; Chem. Eng. News, 2013, 91, 36), motivating us to explore systemically its photocatalytic mechanism under near-infrared light and how to improve and tune its photocatalytic performance. Herein, electronic structures, and effective masses of electron and hole at energy band edges are theoretically investigated by employing spin-polarized density functional theory calculations. The calculated energy band structure supports the absorption spectra of Cu₂(OH)PO₄ in the NIR region corresponding to the electron excitation from the valence band to the unoccupied bands in the gap. Our charge density analysis indicates that the O atoms in the hydroxyl serves as the effective bridge for the favoring separation of the photogenerated electron–hole pairs. Furthermore, the effective masses of electron and hole analysis demonstrate that the separation and transfer of photogenerated carriers along the [011] direction may be more effective than other possible directions. A qualitative comparison of carrier transfer ability along all the directions in the specific planes is displayed by the three-dimensional band structure. Interestingly, the calculated net dipole moment for the two basic units of Cu₂(OH)PO₄, octahedron and trigonal bipyramid, indicate that the macroscopic dipole moment for Cu₂(OH)PO₄ is zero, however, the distorted octahedron unit has a net dipole moment, which enables us to tune the macroscopic dipole moment by doping. The present work provides theoretical insight leading to a better understanding of the photocatalytic performance of Cu₂(OH)PO₄ and it may be beneficial to prepare more efficient Cu₂(OH)PO₄ for NIR light photocatalysis, which will also be helpful to design and prepare novel photocatalysts.