Here, we report a new Ti(IV)-based porous metal-organic framework (MOF) (NTU-9), which displayed strong absorption in the visible region with a bandgap of 1.72 eV. The electronic structure and bandgap were further investigated by DFT calculations. Photoelectrochemical studies indicated that NTU-9 is photoactive under visible light illumination (λ > 400 nm) and acts as a p-type semiconductor. The results demonstrated that Ti(IV)-based MOFs could be promising visible-light photocatalysts for energy conversion and environmental remediation.