The formation process of Pb(Fe2/3W1/3)O3was simplified and the synthesis temperatures were reduced because of the improved reactivity and homogeneity in sol–gel‐derived precursors. No liquid phases appeared in the specimens formulated from clear refluxed solution, whereas they were observed in the specimens prepared from turbid solution containing lead tungstate precipitates. The mixing state of reactants in precursors greatly affected the formation of liquid phases. Pb(Fe2/3W1/3) grains with a characteristic cubic shape were formed from the sol–gel pr