In this paper, the surfactant template approach and in situ plating of metal nanoparticles were used to develop porous lead nanoparticles-modified thiol-functionalized polysiloxane film glassy carbon electrode (PbNPs-SH-PF/GCE). The modification of porous silica thin films by PbNPs made it possible to increase the electroactive area of SH-PF/GC electrodes, which enabled a significant enhancement of the anodic stripping signal of determined Bi(III). This leads to improved bismuth detection limit, opening promising applications in the field of trace analysis. The obtained silica materials were characterized by SEM, TEM-EDS, FTIR analysis and nitrogen sorption measurements. The electrode exhibited a linear behavior in the concentration range of 0.01-0.2 nmol L-1 (30 min.). The LOD was 2.8 pmol L-1 (R-2 = 0.9970). The proposed procedure was validated by comparing the results obtained for natural water samples collected from Bystrzyca and Vistula rivers with those provided by application of ICP-MS method. (C) 2016 Elsevier Ltd. All rights reserved.