Ceramics of the perovskite multiferroics PbFe0.5Nb0.5O3 (PFN) and PbFe0.5Ta0.5O3 (PFT) were synthesized from new citrate polymeric precursors. X-ray tests pointed to trace amounts of the pyrochlore phase. SEM studies revealed the heterogeneous grain size distribution for PFN and the homogeneous one for PFT. Dielectric studies pointed to one diffuse T-C phase transition at 378K for PFN and two diffuse M-T and T-C phase transitions, at 200 and 235K, for PFT, respectively. X-ray photoelectron spectroscopy studies of PFN reveal that all ions exist in one valence state, however, with two chemical shifts for Pb2+. Two valence states for the majority of ions of PFT seem to be connected with a higher volume fraction of the amorphous grain-boundary phase. The electronic energy band gap for both compounds is approximately 2.8eV. Two magnetic transitions, ie, from the paramagnetic to the antiferromagnetic phase and then to the spin-glass phase, were observed at 156 and 10K for PFN, and at 145 and 15K for PFT, respectively.