The application of a solid-state electrochemical technique, voltammetry of microparticles (VMP), for studying archeological lead glass is described. Upon attachment to graphite electrodes immersed into aqueous acetate buffer, characteristic voltammetric profiles were obtained for submicrosamples of archeological glasses dated between the 9th and 19th centuries. Bivariate and multivariate chemometric analyses of the VMP data allowed us to characterize individual workshops/provenances which enabled a clear discrimination between soda-rich and potash-rich glasses. An analysis of the VMP data, combined by XRF, FESEM, AFM and ATR-FTIR and Micro-Raman spectroscopies, denoted the presence of Pb(IV) centers accompanying network-former and network-modifier Pb(II).