The present work involves the synthesis of a series of Sm(2-x)Dy(x)Zr(2)O(7) compounds (0.0 ≤ x ≤ 2.0) by a controlled gel combustion process. The powders were thoroughly analyzed by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy, and diffuse-reflectance UV-visible spectroscopy. The powder XRD studies revealed the system to be single-phasic throughout with retention of pyrochlore-type ordering until 40 mol % of Dy(3+), beyond which the pyrochlore lattice gives way to the defect fluorite structure. Interestingly, Raman spectroscopic studies (as against XRD studies) showed retention of pyrochlore-type ordering throughout the homogeneity range of the compositions studied. This is perhaps the first study that reports retention of a weak pyrochlore-type superstructure in the Dy(2)Zr(2)O(7) system, which was otherwise known to crystallize in the defect fluorite system. The ionic conductivity measurements showed an increase in the activation energy (E(a)) with an increase in the mole percent of Dy(3+) owing to the decreased mobility with an increase in the degree of disorder. The system possesses a tunable band gap with varying amounts of Dy(3+). First-principles calculations were performed to support a decrease in the band gap of the doped system with an increase in the Dy(3+) content. The potential as photocatalysts of some of these compositions was explored, and they exhibited high photocatalytic activity for degradation of xylenol orange, with t(1/2) increasing from pure Sm(2)Zr(2)O(7) to pure Dy(2)Zr(2)O(7).