Three crystallographically different structures of (Fe1−xVx)3 Ge have been studied by57Fe Mossbauer spectroscopy. The hexagonal phase, stable for low values ofx, is ferromagnetic with the spins parallel to thec-axis above a critical temperature, where a spin flip to thec-plane takes place. A V/Fe substitution in the near surrounding of an iron atom leads to a decrease in the isomer shift of −0.02 mm/s and an estimated reduction in the magnetic moment of 0.31μB from 2.07μB. A result for the intermediate cubic closed packed structure is that V populates only one type of metal sites. Furthermore, from similarities withα-Fe the average value of the change in isomer shift is found to be +0.075 mm/s and +0.02 mm/s per Ge/Fe substitution in the 1nn and 2nn shells, respectively. The spin polarization effect on the magnetic hyperfine field for iron is −8.6%, −0.4%, and −0.6% per Ge/Fe (1nn), Ge/Fe (2nn) and V/Fe (3nn) substitutions, respectively. The simple cubic compound (Fe0.7V0.3)3 Ge is non-magnetic down to at least 5 K. Here a decrease in the isomer shift of −0.05 mm/s is found for a V/Fe (1nn) substitution.