In this report, we designed a visible-light sensitive heterojunction photocatalyst by coupling N-TiO2 with Mg3Al0.5Cr0.5O4.5 through in situ growth followed by heat treatment. For the 50% N-TiO2/Mg3Al0.5Cr0.5O4.5 catalyst, the structure, optical properties, and photocatalytic activity for cyclohexane oxidation were systematically investigated. The as-synthesized hybrid heterojunction exhibited enhanced visible-light absorption and fast carrier separation, resulting in significantly improved photocatalytic activity (17.62%) and excellent recyclability (98.6%) for cyclohexane oxidation; these performances mainly resulted from the synergistic effect of N-doping and the construction of a heterojunction. Moreover, X-ray photoelectron spectroscopy further indicated that there were oxygen vacancies in the composite and strong electron interactions between N-TiO2 and Mg3Al0.5Cr0.5O4.5. This promoted the separation of photogenerated charges and enhanced the photocatalytic performance. Therefore, this work opens a new way to fabricate highly efficient photocatalysts toward cyclohexane oxidation under visible light irradiation.