In this study, ternary ferroelectric 0.06Pb(Mn1/3Nb2/3)O3–0.94Pb(Zr0.48Ti0.52)O3 (PMN–PZT) thin film with high piezoelectric coefficient were grown on La0.6Sr0.4CoO3‐buffered Pt/Ti/SiO2/Si substrate by RF magnetron sputtering method. The phase and domain structure along with the macroscopic electrical properties were obtained. Under the optimized temperature of 550°C and sputtering pressure 0.9 Pa, the PMN–PZT film owned large remnant ferroelectric polarization of 62 μC/cm2. In addition, the PMN–PZT film had polydomain structures with fingerprint‐type nanosized domain patterns and typical local piezoelectric response. Through piezoelectric force microscopy, the PMN–PZT thin film at nanoscale exhibited obvious domain reversal when subjected to in situ poling field. It was further found that the quasi‐static piezoelectric coefficient of the PMN–PZT thin film reached 267 pC/N, which was about twice to that of the commercial PbZrO3–PbTiO3 (PZT) thin film. The optimized relaxor ferroelectric thin film PMN–PZT on silicon with global electrical properties shows great potential in the piezoelectric micro‐electro‐mechanical systems applications.