The photo-/electrocatalysts with high activities for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) are of significance for the advancement of photo-/electrochemical energy systems such as solar energy to resolve the global energy crisis, reversible water electrolyzers, metal–air batteries, and fuel cells. In the present work, we have systematically investigated the photochemical performance of the 2D β-antimonene (β-Sb) monolayer. From density functional theory investigations, β-Sb with single-atom doping possesses a trifunctional photocatalyst with high energetics and thermal stabilities. In particular, it is predicted that the performance of the HER activity of β-Sb will be superior to most of the 2D materials. Specifically, β-Sb with single atom replacement has even superior that the reference catalysts IrO2(110) and Pt(111) with relatively low overpotential values for ORR and OER mechanisms. The superior catalytic performance of β-Sb has been described by its electronic structures, charge transfer mechanism, and suitable valence and conduction band edge positions versus normal hydrogen electrode. Meanwhile, the low overpotential of multifunctional photocatalysts of the Bi@β-Sb monolayer makes them show a remarkable performance in overall water splitting (0.06 V for HER, 0.25 V for OER, and 0.31 V for ORR). In general, the Bi@β-Sb monolayer may be an excellent trifunctional catalyst that exhibits high activity toward all electrode reactions of hydrogen and oxygen.