Relaxor ferroelectric compositions of 0.2Pb (Mg 1/3 Nb 2/3 )O 3 -0.5Pb(Zr 0.48 Ti 0.52 )O 3 -0.3Pb(Fe 1/3 Nb 2/3 ) O 3 (0.2PMN-0.5PZT-0.3PFN) ceramics were doped with different concentrations of Li 2 CO 3 and were prepared by a columbite precursor process. Their structural, dielectric and pyroelectric properties were studied. A phase analysis was performed using the X-ray diffraction patterns from 2θ=44°t o 46°, over which the tetragonal phase displays two peaks, (002) T and (200) T , while the rhombohedral phase displays one peak, (200) R . A well saturated P-E hysteresis loop was obtained for the 0.2PMN-0.5PZT-0.3PFN ceramic doped with 0.2 wt.% Li 2 CO 3 , and the values for the remnant polarization (P r ) and coercive field (E c ) were 30 μC/cm 2 and 5.4 kV/cm, respectively. A maximum value of the pyroelectric coefficient, 518 μC/m 2 K, was obtained for the 0.2PMN-0.5PZT-0.3PFN ceramic doped with 0.3 wt.% Li 2 CO 3 at the maximum temperature (T max ) due to the decrease of the binding energy for the polarization charge which in formed at the surface.