In this study, boron doped calcium stabilized bismuth cobalt oxide nanocrystalline ceramic powders were successfully prepared from aqueous boric acid containing calcium-bismuth-cobalt acetate/poly(vinyl alcohol) hybrid precursor polymer solutions. Then, obtained ceramic powders were characterized via FT-IR, XRD, and SEM techniques. According to X-ray results, fcc and bcc phases coexist in the samples of the nanocrystalline ceramic powders. fcc peaks became sharper and bcc peak decreased with increasing boron content. Structural parameters for face centered cubic structure were calculated using the Scherrer equation. Moreover, dislocation densities and microstrain values were calculated for the nanocrystalline powder samples. © 2012 Elsevier Ltd and Techna Group S.r.l.