We report on the results of low-temperature stimulated Raman scattering (SRS)-spectroscopy of tetragonal GdVO4 single crystals. Measurements at T ≈ 9 K and picosecond excitation in the visible and near-infrared range revealed new manifestations of χ(3)-nonlinear photon–phonon interactions. Besides many-phonon Stokes and anti-Stokes octave spanning SRS generation we discovered a new fundamental χ(3)-active phonon mode of the crystal. Furthermore, we received data on combined SRS-active vibrational modes. The lower limits of the steady-state Raman gain coefficients for first Stokes generation have been estimated together with the temperature dependence of these values in the range from T ≈ 9 and 273 K. A short review of SRS-promoting vibrational modes and manifestations of χ(3)-nonlinear interactions of all known SRS-active tetragonal rare-earth REVO4 vanadates is given as well.