Polycrystalline rare‐earth orthoferrites (LnFeO3) in which some Fe3+ has been replaced by M2+ (M2+ = Ni, Mn, Cu and Co) have been prepared. Charge compensation was effected by the substitution of F− for O= to give the general formula LnFe1−xM+2xO3−xFx. X‐ray techniques and magnetic measurements of Curie points were used to verify the absence of second phases. Materials of the type LnFe0.8Ni0.2O2.8F0.2 (Ln = Y, La–Yb) exhibited room‐temperature magnetic moments which were of the order of four times larger than those of the unsubstituted orthoferrites, implying marked increases in canting angle. Curie temperatures decreased about 20°C. Where Ln = Sm the limit for Ni2+ – F− substitution was x ≈ 0.2. For Ln = Ho the substitution limit was x ≈ 0.3. In both cases increasing Ni2+–F− substitution resulted in increasing magnetic moment. When the substituted orthoferrites contained Cu2+ and F− no large changes in magnetic moment or Tc were observed. For Mn2+–F− substitution the Curie temperature decreased about 30°C and the magnetic moments varied irregularly for different rare‐earth orthoferrites. Co2+–F− containing orthoferrites were prepared and were single phase with respect to x‐ray measurements, however a large magnetic impurity developed during high temperature magnetic measurements. We were unable to prepare pure Fe2+ containing orthoferrites. The enhanced moments obtained with Ni2+–F− substitution would result in useful decreases in ``bubble'' domain diameter in single crystals of these materials.