The analytical methods used to determine germanium must be very sensitive as the germanium content in natural materials and waste rarely exceeds the mg/kg level. Among the numerous analytical techniques available, catalytic adsorptive stripping voltammetry (CAdSV) plays an essential role due to its remarkable sensitivity. After careful selection of the catalytic reagent and electrode material, the detection limits at sub-nM level are feasible. In the present work, it has been shown that the properties of lead and bismuth plated electrodes (plating solutions: quiescent 0.34 M HClO₄ containing 0.043 M of Bi(III) or stirred 0.2 M acetate buffer containing 0.003M Pb(II), E_plat = -0.9 V, Q_plat = 0.8 mC per mm²) differ considerably and only bismuth film electrodes enable germanium analytical signals to be obtained when Ge(IV)-catechol-V(IV)-HEDTA (HEDTA - N-hydroxyethyl-ethylene diamine-triacetic acid) catalytic system is employed. The bismuth film electrodes deposited on screen-printed carbon (Bi/SPE) supports provided well-shaped, sensitive, and reproducible signals of Ge(IV) (RSD = 2%) in the supporting electrolyte containing 0.05 M acetate buffer (pH of 4.4), 1 mM of catechol, 1 mM of V(IV) and 1.5 mM of HEDTA. The calibration curve was linear within the range from 2 to 30 nM of Ge(IV) (LOD = 1.5 nM). The applicability of the Bi/SPE electrodes was verified by measuring Ge(IV) in spiked snow water samples. The concentration determined by the standard addition method was equal to 10.05±0.11 nM of Ge(IV) that correlates well with the spiked value equal to 10 nM of Ge(IV).