A modified sol–gel processing has been developed by using polyvinylpyrrolidone (PVP) as modifier and lead nitrate as lead source to synthesize (1−x)Pb(Mg1/3,Nb2/3)O3−xPbTiO3 (PMN–PT) thin films with x=0.23–0.43. The composition distribution and morphology of the gel particles in the PMN–PT solutions have been investigated. It shows that PVP addition results in spatial separation between Pb and Nb ions in the gel particles, leading to the perovskite crystallization via a columbite‐like route in the resultant PMN–PT thin films. Pyrochlore phase is circumvented and perovskite phase can directly crystallize from amorphous films at the temperature as low as 460°C, while in the non‐PVP films, B‐site rich pyrochlore phase (Pb1.83Nb1.71Mg0.29O6.39) is always formed in the temperature range used (460°–650°C).