To study the multiferroic behavior of BiFeO3 at low concentrations of Mn as dopant, BiFe1−xMnxO3 (BFMO) at x = 0.01, 0.02, and 0.03 has been successfully synthesized via chemical combustion method. X-ray diffraction reveals distorted rhombohedral structure for BiFeO3 and respective variation in lattice parameters. The particle size is studied with FESEM images. Wide-range frequencies are used to carry out dielectric constant and tan δ (loss factor) measurements. The typical behavior of BFMO samples is attributed via charge-carrier hopping mechanisms due to structural inhomogeneity and formation of vacancies. The hysteresis loop measurements are used to study the ferroelectric and magnetic response. The canting of spin moments and cation–anion–cation exchange interactions leads to observed room-temperature ferromagnetism, while ferroelectric performance enhances with increasing Mn doping in BiFeO3. The altered ferroelectric and magnetic properties along with possible magnetoelectric coupling would make BFMO as suitable candidate for magnetoelectric devices. The maximum value obtained for $${\alpha }_{\text{ME}}$$ is 29.03 mV cm−1Oe−1 at Hdc = 1.4 kOe and could be attributed due to strong antiferromagnetic character of BFO with Mn doping.