Cu doped crystalline SiO₂ in various phases viz. coesite, pyrite, and cristobalite has been successfully synthesized through the chemical route. All the studied samples show mixed phases and the relative contribution is found to be dependent on the annealing temperature. For sample heated at 300°C the most dominant phase is Coe site where as for samples heated in the temperature range 500–900 °C the dominant phase is pyrite along with the quartz, coesite and cristo balite phase. The Cu⁺ emission intensity as well as wavelength in all these samples is found to be dependent on the dominant phase as well as relative contribution of otherless dominant phases. For sample heated at 300 °C in which dominant phase is coesite the emission is observed around 360nm. The samples which are heated in the temperature range 500–900 °C in which dominant phase is pyrite shows double humped emission with peaks around 360nm and at 395nm. The study shows that cristo balite phase is detrimental to Cu⁺ luminescence. Samples in which cristo balite phase is present in large amount, less intense Cu⁺ luminescence is observed. The TL/OSL also follows the similar trend. Of the several samples, maximum TL/OSL sensitivity is obtained for the 700 °C heated sample for which the relative contribution of cristo balite phase is minimum. On the basis of an area integration method ; integrated over initial 3 s, the OSL sensitivity in this sample is found to be 2.3 times the sensitivity of commercial Al₂O₃:C.