Positron lifetime (LT) and coincidence Doppler broadening (CDB) measurements on nanopowders and ceramics of ceria- and magnesia-stabilized zirconia (CeSZ and MgSZ, respectively) are presented. The nanopowders were prepared by the coprecipitation technique. Effects of nanopowder calcination and sintering at various temperatures were investigated. In the nanopowders, the two kinds of open-volume defects associated with grain boundaries (GBs) could be identified via positron trapping: (i) vacancy-like misfit defects situated along GBs and (ii) larger defects at the intersections of at least three GBs (triple points). CDB measurements on CeSZ compacted nanopowders indicated a segregation of Ce ions along GBs. A few percent fractions of positrons were found to form positronium localized in pores of ≈1.8 nm diameter in compacted nanopowders. Sintering of nanopowders at 1500°C appeared to be sufficient for disappearance of pores and triple point defects. In sintered ceramics, contrary to compacted nanopowders, positrons were trapped in zirconium vacancies in grain interiors.