We report on the mechanisms responsible for the formation of optical waveguides upon femtosecond laser irradiation of an alkaline lead-oxide silicate glass. MicroRaman spectroscopy and nonlinear fluorescence were employed to probe the local glass network structure and the formation of optically active defects respectively. At low laser pulse energies, the laser modified region is formed by a single light guiding region, whereas for pulses above 14 μJ the modified region is formed by a central dark zone, which does not guide light, accompanied by light guiding zones located in the surrounding of the dark one. This behavior is different from that observed in common silica glass systems but agrees with recent results obtained in phosphate and heavy metal oxide glasses. However, our results show that, unlike the latter glass, local densification of the glass occurs in the whole laser modified region, i.e., in the dark and the guiding zones. The suppression of light guiding in the dark region is explained by a high density of absorbing color centers.