Crystal structures and microstructures associated with ferroelectric properties in a lead-free piezoelectric compound, x(Bi0.5K0.5)TiO3–(1-x)BiFeO3, have been investigated mainly by transmission electron microscopy (TEM). Complicated ferroelectric domain structures with a width of approximately ∼200 nm were found in the polar rhombohedral structure of the x = 0.30 compound. On the other hand, a tweed-like contrast, which stems from local lattice distortion, was observed in the pseudocubic structure of the x = 0.40, 0.46, and 0.50 compounds. The present results suggest that the pseudocubic phase is characterized by nanodomain structures consisting of non-polar cubic and polar rhombohedral structures.