Lead-free (Ba0.91Ca0.09Sn0.07Ti0.93)O3 (BCST) ceramics, doped with holmium (Ho) in the range 0–1.0 mol%, were synthesized using conventional solid-state sintering method. XRD analyses of these ceramic samples confirm single phase pure perovskite structure. Evidence of Ho3+ substituting Ba2+ via electronic charge compensation exists in the range 0–0.4 mol%, while ionic charge compensation mechanism dominates beyond 0.4 mol%. Crystallite size and lattice strain undergo systematic change, while the room temperature dielectric constant (εrt) decreases with increasing Ho content. The Curie temperature Tc and maximum dielectric constant (εm) at Tc remain almost unchanged. Remnant polarization (Pr), electromechanical coupling constant (kp) and piezoelectric charge coefficient (d33) exhibit increasing trend with increasing Ho content and reach their maximum values of 8.2 µC/cm2, 25% and 220 pC/N respectively at 1.0 mol% of Ho content. The study reveals that doping of BCST system with appropriate quantity of Ho can improve its ferroelectric and piezoelectric properties.