The Mössbauer spectra of Fe in Fe3-xVxSi alloys for 0≤x≤1 shows that V occupies almost exclusively one of two Fe sites (the B site). As x increases the spectra of Fe on the other site (the A, C site) becomes increasingly complex as the number of their V 1st neighbors increases. Simulated Mössbauer spectra were calculated using moments obtained by a simple model from bulk magnetization and V NMR data. This model assumes a decrease in Fe(A, C) moments as the number of their Fe 1st neighbors decreases. Comparison of the Fe(B) field of the alloy with x=1 to that of the alloy with x=0 gives an estimated reduction in the on site 4s electron polarization of about 100 kOe or about 0.05 unpaired 4s electrons