The commonly used electrodeposition method for copper electrorefining electrolyte purification is actually suffered from the complicated process, expensive energy cost and the potential arsine hazard. This work synthesized a kind of submicro-sized amorphous antimonic acids (A-SbA) with ultrahigh solubilities in strong acid aqueous solution and evaluated their environment-friendly application in removing the problematic impurity bismuth (Bi). By controlling the hydrolysis ratio and aging time the crystalline structures and dissolution behaviors of A-SbA materials can be varied. The effects of hydrolysis ratio, aging time, temperature, acidity, initial Bi concentration and co-existing ions on Bi(III) removal efficiencies by A-SbA were systemically studied. The results show that the A-SbA prepared at a hydrolysis ratio of 1:2 without aging treatment has the highest solubility and the maximum Bi(III) removal capacity can reach 300.2 mg g^-1. The Sb(V)-Bi(III) reactions follow a pseudo-second-order kinetics model and the apparent activation energy of reaction process is calculated to be 32.14 kJ mol^-1. The Bi(III) removal efficiencies of over 99% can be achieved under the coexistence of Cu²⁺, Ni²⁺, Na⁺ and Sb(III), while As(III,V) ions can also be partially precipitated together with Bi(III). This work gives an insight into the hydrolysis of antimony pentachloride and the polymerization of monomer HSb(OH)₆ as well as the Sb(V)-Bi(III)-As(III,V) interaction behaviors.