The poor catalyst stability in acidic oxidation evolution reaction (OER) has been a long-time issue. Herein, we introduce electron-deficient metal on semiconducting metal oxides-consisting of Ir (Rh, Au, Ru)-MoO3 embedded by graphitic carbon layers (IMO) using an electrospinning method. We systematically investigate IMO’s structure, electron transfer behaviors, and OER catalytic performance by combining experimental and theoretical studies. Remarkably, IMO with an electron-deficient metal surface (Irx+; x > 4) exhibit a low overpotential of only ~156 mV at 10 mA cm-2 and excellent durability in acidic media due to the high oxidation state of metal on MoO3. Furthermore, the proton dissociation pathway is suggested via surface oxygen serving as proton acceptors. This study suggests high stability with high catalytic performance in these materials by creating electron-deficient surfaces and provides a general, unique strategy for guiding the design of other metal-semiconductor nanocatalysts.