Lanthanum zirconate (La2Zr2O7=LZO) pyrochlores doped with varying concentrations of Eu were synthesized using a low temperature gel-combustion synthesis route and characterized using X-ray diffraction, scanning electron microscopic and photoluminescence techniques. The final annealing temperature of the system could be brought down to 700°C to produce a single phase compound. In addition, the optimum activator ion concentration for maximum luminescence yield was evaluated for the system. The site occupancy for the Eu ions was also investigated which suggested that at 500°C, the ions were on the surface of the LZO host and later diffused into the lattice and replaced the La3+ ions on annealing at 700°C 5h. However, due to difference in the ionic radii, the doped RE ions were of the inversion center forming a D2d symmetry around them. For the first time the radiative properties and the commercial utility of the LZO system have been investigated. These parameters were used to get an idea about the M–L bond covalency in the system. The radiative properties suggested the system can be used as a potential ‘red’ emitting phosphor.