The paper describes studies on surface atomic composition, microstructure and microarea elemental distribution in sintered undoped as well as donor or acceptor doped polycrystalline barium titanate ceramics. The specimens examined are derived from barium titanate powders synthesized by two different wet chemical procedures namely oxalate precursor route and gel-to-crystallite conversion. The compositional analysis is carried out by backscattering spectrometry (BS) involving 3.05 MeV O-16(alpha,alpha)O-16 resonant scattering while investigations on microstructure and microarea elemental distribution are performed using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), respectively. The specimens prepared by either method are monophasic; however, their surface atomic composition, microstructural features as well as electrical characteristics are significantly different. The specimens obtained by oxalate precursor route generally have Ti rich surfaces and exhibit coarse to fine grained microstructure depending on the nature and extent of doping. The Mn-doped specimens exhibit appreciable O deficiency. The specimens prepared by gel to crystallite conversion, in contrast, usually have Ba enriched surfaces and exhibit fine-grained microstructure. EDS measurements show the segregation of acceptors such as Mn, Cu and Zn in the grain boundaries of oxalate precursor derived ceramics. Further, the relative atomic ratio of Ti to Ba at the sites of segregations is higher compared to other locations.