The pre-deposition of Sn following with the square-wave anodic stripping voltammetric (SWASV) analysis is employed to determine the Sn 2+ -sensing ability of bismuth-film electrodes (BFEs). The influences of Bi microstructures, such as grain size, preferred orientation ratio between Bi(110) and Bi(012) (denoted as f), and average roughness factor (Ra) of Bi deposits on the Sn 2+ -sensing ability, are investigated. The preferred orientation ratio is a key factor determining the Sn 2+ -sensing ability of BFEs meanwhile a synergistic effect between grain size and f on enhancing the current density of Sn 2+ sensing is obtained when f is above 0.11. The crystalline facet of Bi(110) favorable for pre-depositing Sn is the main reason enhancing the Sn 2+ sensing of Bi deposits. Thus, this work shows that Sn 2+ sensing through stripping of pre-deposited Sn on BFEs does not follow the mechanism of forming Bi-alloy amalgams since the successful pre-deposition of trace Sn 2+ on Bi strongly depends on the effective exposure of crystalline facet of Bi(110).