A series of rare-earth zirconate RE 2Zr 2O 7 nanocrystals (RE = La, Nd, Eu and Y) were prepared by a simple combustion method. These compounds possess either a pyrochlore structure (P-RE 2Zr 2O 7) or a defect fluorite structure (F-RE 2Zr 2O 7), which depends on the ionic radius of RE 3+. The photoluminescence (PL) property of the as-prepared RE 2Zr 2O 7 nanocrystals was studied, and the observed emissions in the UV and visible range were attributed to different transition mechanisms for RE 2Zr 2O 7 with different RE ion. A PL mechanism has been proposed, associated with the transition between the valence band and a mid-gap state related to oxygen vacancies. Divalent Pb ions were introduced into RE 2Zr 2O 7 nanocrystals and the luminescence of the Pb 2+-doped samples was also recorded for comparison. The PL property of RE 2Zr 2O 7 was found to be intimately related to their intrinsic defect structure, and PL was thought as a new method to estimate the degree of disorder in the A 2B 2O 7 structure (from pyrochlore structure to defect fluorite structure).