A series of Bi 1−x Ca x FeO 3 (x=0.1, 0.3, 0.5) multiferroic samples have been prepared in order to study the effect of different concentrations of Ca on the crystal structure, and dielectric properties. Structural analysis has been performed using X-ray diffraction (XRD) measurements. Rietveld refined XRD data confirm that all the samples are of single phase, having hexagonal structure with R3c space group. Cell parameters decrease systematically with increase in Ca concentration. Dielectric measurements have been performed in the temperature range of 200–450K at selected frequencies in the range 100–1100kHz. A near room temperature ferroelectric anomaly has been observed in all the samples which shift toward lower temperature with increase in doping. Conduction activation energies are calculated and found to decrease with increasing doping.