The selective oxidation of hydrocarbons (RH) by dioxygen (O2) is a very important method for industrial production of bulk oxygen-containing compounds, However, due to the high chemical inertness of RH and O2, achieving this reaction under mild conditions still faces significant challenges. This paper discloses an efficient hybridizing engineering (HE) strategy of decatungstate (DT) with 3d transition metal ions (Mn+=Ni2+, Co2+ or Cu2+)-modified carbon quantum dots (Mn+/CQD) as the dopants. Compared to pure CQD, The Mn+/CQD can more efficiently combine with DT anion to fabricate a high-quality hybrid via electrostatic interactions, thereby bestowing the hybrid with an enhanced visible light response especially the separation efficiency of photo-generated charge pairs. Furthermore, the above hybridization effects of Mn+/CQD on DT anion can be fine-tuned and gradually improved with a change of the metal ion from Cu2+, Co2+ to Ni2+, along with a continuous enhancement of the hybrid's photo-catalytic efficiency in the visible light- triggered selective oxidation of ethylbenzene with O2 in acetonitrile. The best Ni2+/CQD-doped TBADT can achieve ca. 48% ethylbenzene conversion and 87.6% acetophenone selectivity in the presence of 2 M HCl, and it also shows a much higher photo-catalytic activity for the photo-oxidation of toluene, cyclohexane and benzyl alcohol compared to pure TBADT. The HE strategy with Mn+/CQDs as the cationized hybridizers is much superior to that with pure CQD or Ni2+ as the hybridizer in hoisting the photo-catalytic performance of DT.