The phase formation, sintering behavior and microwave dielectric properties of Bi2O3 and MnO2 co-doped [(Pb, Ca) La](Fe, Nb)O3+delta (PCLFN) ceramics were investigated. The Bi2O3 and MnO2 binary dopants formed stable and low melting temperature solubilities at grain boundary which resulted in an effectively lowered sintering temperature by about 140 degrees C a more rapid sintering process and enhanced bulk densities. Sintering procedure has significant effect on grain size and porosities in ceramics. With high sintering temperature and time, the evaporation of PbO scaled up from surface toward the bulk and resulted in a Pb2+ deficient layer up to 0.25 mm depth under ceramic surface. Investigation of sintering dynamic revealed that either volume diffusion or second-order interface mechanism controlled the grain growth in present system. An optimal microwave dielectric properties of epsilon(r) = 91.1, Q (f) = 4,870 GHz and tau (f) = 18.5 ppm/degrees C could be obtained in Bi2O3 and MnO2 co-doped [(Pb, Ca) La](Fe, Nb)O3+delta ceramics sintered at 1,050 degrees C for 4 h when the quality ratio of Bi2O3/MnO2 was 1 and the doping content w = 1 wt%.