Present work investigates the detailed multiferroic properties of Pb1 − xSmxTi1−xFexO3, (x = 0.21, 0.22, 0.23, 0.24 and 0.25) synthesize through solid state reaction route. The structural, dielectric, ferroelectric and magnetic properties were measured. A sincere study is carried out to detect the magneto-electric coupling in all the samples through magneto-dielectric, magnetization after electric poling and magneto-pe response. The maximum value of coupling coefficient (γ) and magneto-dielectric response (MDR) of sample x = 0.24 has shown by magneto-dielectric properties and magnetization after electric poling whereas magneto-pe has shown that all the samples possess multiferroic nature.