The results of a Mossbauer study of the magnetic structure of multiferroic BiFe0.80Cr0.20O3 in the temperature range of 5–550 K are presented. It is found that a collinear antiferromagnetic structure of the G type is present in BiFe0.80Cr0.20O3 at temperatures below 260 K. Above 260 K, an anharmonic spin wave with a magnetic anisotropy of the easy-axis type with a high value of the anharmonicity parameter m arises. With a further increase in the temperature, the m parameter decreases and tends to zero at T ~ 420 K, at which a harmonic spin wave comes into existence. Above a temperature of about 420 K, the m parameter increases again and the spin wave becomes anharmonic with an easy-plane magnetic anisotropy. At the Neel temperature, TN = 505 ± 10 K, the sample undergoes a transition from the magnetically ordered to the paramagnetic state. The change in the type of magnetic anisotropy at T ~ 420 K is explained by competing contributions of different signs to the effective magnetic anisotropy constant and their different temperature dependence for the BiFe0.80Cr0.20O3 multiferroic.