Nonoxidative propane dehydrogenation (PDH) has become a more attractive process worldwide because of the low cost and abundance of shale gas that has recently become available. Orthodox catalysts for PDH based on Pt and CrOx face challenges because of the high cost of the former and the toxicity of the latter. Herein, we present defective TiO2 -based catalysts for the PDH reaction, which are inexpensive and eco-friendly. Comprehensive characterizations of their structure, morphology, and surfaces reveal that the fourfold-coordinated titanium atoms surrounding oxygen vacancies (OVs) are the main active sites for PDH. Density functional theory calculations have been employed to further explain the superior catalytic properties of defective TiO2 for PDH. Experimental results have demonstrated that the catalytic performance of PDH was significantly improved using TiO2 subjected to a reduction treatment. Moreover, the hydrogen reduction temperature for pristine TiO2 was found to influence the catalytic performance.