Constructing robust and cost-effective Pt-based electrocatalysts with an easily operated strategy remains a crucial obstacle to fuel cell applications. Conventional Pt-based catalysts suffer from high Pt content and an arduous synthetic process. Herein, through the spray dehydration method and annealing treatment, facile producible synthesis of a small-sized (5.2 nm) low-Pt (10.5 wt %) ordered PtCo3/C catalyst (O-PtCo3/C) for oxygen reduction reaction is reported. The fast spray evaporation rate contributes to small size and uniform nucleation of nanoparticles (NPs) on carbon support. O-PtCo3/C-600 exhibits efficient electrocatalytic performance with mass activity (MA) 6.0-fold and specific activity 3.9-fold higher than commercial Pt/C. The ordered chemical structure generates superior stability with merely 3.5% decay in MA after 10,000 potential cycles. Density functional theory calculations reveal that the enhanced catalytic performance originates from rational modification of d-band through strain and ordering effect and accompanying weaker adsorption of intermediate OH. This work highlights the potentials of low-Pt PtM3-type ordered NPs for prospective fuel cell cathodic catalysis. The proposed facile and practical synthetic strategy also shows promising prospects for preparing effective Pt-based electrocatalysts.