Abstract The initial electrocrystallization of As–Sb alloy on glass carbon (GC) electrode in hydrochloric acid system was studied via cyclic voltammetry (CV) and chronoamperometry measurements. Current transients were presented in dimensionless formation, which showed that the initial nucleation/growth process of As–Sb alloy followed three-dimensional nucleation model with diffusion-controlled growth. Relevant nucleation parameters were calculated by analyzing related current transients. Particular attention was paid to the effect of Sb(III) concentration on the nucleation process during the co-electrodeposition. The quantitative results showed that Sb(III) played a positive effect on enhancing the nucleation rate of As–Sb alloy, leading to the evolution of alloy surface morphology from grain structure to compact layer structure.