A novel solid bismuth microelectrode in combination with adsorptive stripping voltammetry is demonstrated as a simple and fast method for determination of tin. The proposed method includes the formation of a tin complex with cupferron in the solution and deposition on the solid bismuth microelectrode. The selection of the most optimal parameters determining the sensitivity of the elaborated procedure was made. Under optimized parameters (pH = 4.6; acetate buffer concentration: 0.1 mol l−1; cupferron concentration: 2 × 10−4 mol l−1; activation potential/time: −2.5 V/5 s; deposition potential/time: −0.6 V/40 s), a linear response of Sn(II) in the concentration range of 8 × 10−9 do 8 × 10−7 mol l−1 (r = 0.9984) was obtained with a detection limit of 2.1 × 10−9 mol l−1. The interferences of foreign ions and organic matrix of environmental water samples were carefully studied. The accuracy of the method was studied by analyzing certified reference materials SPS-WW1 Waste Water and SPS-SW1 Surface Water as well as Bystrzyca river and rain water, and passable results were obtained.