Porous NiTiO₃ nanorods have been successfully synthesized by an ethylene glycol-mediated route at room temperature followed by calcination at 600 °C in air. Characterisation results reveal that the obtained NiTiO₃ nanorods are 3 μm in length and 400 nm in diameter. They possess rough surfaces and accumulation holes, which are beneficial for adsorption and thereby superior for photocatalysis. The porous NiTiO₃ nanorods possess a noticeable optical absorbance in the visible range, indicating they have visible light photoresponse. The photocatalytic activity is evaluated in the degradation of nitrobenzene, which is a highly toxic organic pollutant in wastewaters. The porous NiTiO₃ nanorods exhibit better photocatalytic activity under visible light irradiation than that of NiTiO₃ nanoparticles and commercial TiO₂ (Degussa P25). The enhancement is attributed to the porous texture, which offers more active sites and facilitates mass transport, and the special 1D structure that favors the separation of photogenerated electron–hole pairs, which is confirmed by surface photovoltage spectra.