We report the Cr3+ for Mn3+ substitution in the BiMnFe2O6 structure. The BiCrxMn1−xFe2O6 solid solution is obtained by the solution–gel synthesis technique for the x values up to 0.3. The crystal structure investigation using a combination of X-ray powder diffraction and transmission electron microscopy demonstrates that the compounds retain the parent BiMnFe2O6 structure (for x = 0.3, a = 5.02010(6)Å, b = 7.06594(7)Å, c = 12.6174(1)Å, S.G. Pbcm, RI = 0.036, RP = 0.011) with only a slight decrease in the cell parameters associated with the Cr3+ for Mn3+ substitution. Magnetic susceptibility measurements suggest strong similarities in the magnetic behavior of BiCrxMn1−xFe2O6 (x = 0.2; 0.3) and parent BiMnFe2O6. Only TN slightly decreases upon Cr doping that indicates a very subtle influence of Cr3+ cations on the magnetic properties at the available substitution rates.