As an attractive and environmentally friendly process for propylene oxide (PO) production, direct epoxidation of propylene (DEP) with molecular oxygen catalyzed by metal-based catalysts such as Ag and Cu has drawn much attention, but remains one of the biggest challenges in chemistry. In this work, the crucial competitive reactions of propylene α-H stripping (AHS) versus the oxametallacycle formation (OMMP formation) using adsorbed atomic oxygen (O∗) or adsorbed molecular oxygen (O 2 ∗) as an oxidant are extensively compared on IB group metal surfaces (Cu, Ag and Au) with varied electronic and structural effects in order to explore the possibility to enhance the PO selectivity by virtue of first-principles calculations. The determining factor for the PO selectivity is quantitatively revealed: it is found that with atomic O∗, the AHS pathway was preferred, indicating the reason for low PO selectivity with current catalysts. By contrast, the undissociated molecular O 2 ∗ species is found to prefer to electrophilically attack the CC double bond of propylene and form a special oxametallacycle intermediate (OOMMP) rather than nucleophilically abstracting the α-H. This OOMMP can readily cleave the O-O bond and transform into OMMP. These results demonstrate that the presence of undissociated O 2 ∗ can efficiently promote the PO selectivity. Furthermore, the merit of such a molecular O 2 ∗ mechanism can be rationalized by our quantitative barrier decomposition analyses, which reveal that the lower hydrogen affinity (ΔE H ) of the O 2 ∗ species dominantly contributes to the limited AHS reaction, and boosts the OMMP selectivity. Therefore, ΔE H can be applied as a selectivity descriptor. An efficient strategy to promote PO formation is presented. The insight obtained could pave the way for further development of catalysts for propylene epoxidation. © the Owner Societies 2017.