Polycrystalline BiFeO3 and Bi0.90Ho0.10FexSc1−xO3 (x = 0, 0.05 and 0.10) compounds were prepared using solid-state reaction method. The structural characterizations indicated that BiFeO3 crystallized in R3c rhombohedral structure whereas a trace amount of orthorhombic Pnma phase was evolved in the Ho and Sc substituted compounds along with major R3c rhombohedral structure. Enhanced and peculiar variations of magnetic properties were observed in Ho and Sc substituted BiFeO3 compounds. Interestingly, the appearance of normal and inverse magnetocaloric effects was investigated in Bi0.90Ho0.10Fe0.90Sc0.10O3 compound. Also, prominent maximum magnetic entropy change of 0.78 J/Kg K was observed at 18 K. Further, both normal and inverse magnetocaloric effects were observed under the fields of 1 T and 2 T, whereas the normal magnetocaloric effect was observed for the fields above 2 T in the low temperature. The second-order magnetic transition was observed in Bi0.90Ho0.10Fe0.90Sc0.10O3 compound from Arrott plot and |ΔSMax| vs H2/3 plot. © 2021, The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature.