The phase relationships in the CaHfTi2O7-GdTi2O7 (zirconolite-pyrochlore) pseudobinary system were investigated, after beating at 1500degreesC, because of their importance in the design of pyrochlore-rich titanate ceramics for immobilization of impure surplus plutonium. Up to 15 mol% of MgTi2O5 and Al2TiO5 were added to CaHfTi2O7-Gd2Ti2O7 compositions to elucidate the effects of divalent and trivalent impurities on the phase stability within these systems. From X-ray diffractometry analysis, scanning electron microscopy, and energy dispersive X-ray spectrometry, phase formation and compositional stability limits were evaluated. The main phases observed in these systems were pyrochlore, perovskite, and polytypes Of zirconolite. The formation of the 2M-, 4M-, and 3O-zirconolite polytypes was dependent on the amount of aluminum or magnesium present. In the magnesium system, a large area of pyrochlore-only was observed, which indicated that divalent impurities of appropriate ionic size could be readily incorporated in the eightfold site of the pyrochlore. The locations of the tentative phase boundaries are discussed with respect to the chemical composition.