Solid solution of (1-x)LaCrO3-xBiCrO(3) (x = 0, 0.10, 0.15, 0.20 and 0.25) was prepared via the citrate-nitrate combustion synthesis. Pure perovskite phase was obtained at 800 degrees C, a much lower synthesis temperature than that needed in the solid-state reactions. The thermodynamics of phase formation and the ceramic sintering mechanism were investigated. The substitution of Bi3+ for La3+ was found to give a separate exothermic decomposition event in the gels and the precursor did not produce a transient liquid phase while heating to 1200 degrees C, as was found in ceramics prepared by solid state reaction. This finding shows that the role of Bi2O3 in the sintering of the La1-xBixCrO3 ceramics depends on the processing method.