Although all kinds of the promising catalytic approaches have been developed in recent years, pursuing a complete green catalytic system with high efficiency for the production of various aldehydes is still an interesting challenge. Moreover, the low chemo-selectivity or chemical deactivation for particular primary aldehydes with complicated substituent groups, however, is an inevitable bottleneck for achieving industrial application. Here, we construct a new green pathway in which carbonate-like species doped TiO2 (C/T) can function as a photocatalyst to exhibit excellent chemoselectivity and stability toward aerobic oxidation of structurally diverse and dysfunctional alcohols (20 examples) with dimethyl carbonate as a green reaction solvent. The control experiments with various species scavengers reveal the role of the active species in the photocatalytic system, and the ESR results further confirm O2(center dot-) as the dominate oxidative species for the reaction. Through that the plausible reaction mechanism for the photocatalytic selective oxidation of alcohols over the C/T catalysts is proposed. (C) 2017 Elsevier B.V. All rights reserved.