Pyrochlore structured compounds form a special class of ceramics as host matrices in phosphors with better luminescent properties. In the present work, the optical properties of pyrochlore oxide Gd2-xTbxTi2O7 (0 ≤ x ≤ 0.16) were investigated and linked with structural properties via examination of structural distortion produced with the doping of rare-earth element. These oxide compositions were produced through standard solid-state reaction method. The investigations using advanced characterization techniques; X-ray diffraction and Raman spectroscopy give a signature of single phasic pyrochlore structure in the synthesized samples optimized through multiple heating protocol. The diffraction patterns and Raman spectra, both were continuously being shifted towards lower 2θ value and lower wave-number side, respectively with the doping concentration which can be interpreted by the production of defects in cationic lattice. A similar decreasing trend in particle size has been observed from W–H plot (728 Å to 616 Å) and Scanning electron micrographs (0.82 μm–0.78 μm) with the introduction of Tb3+ ion. The band-gap for the host matrix Gd2Ti2O7 through UV absorption pattern came out to be 2.26 eV. From photoluminescence excitation (λem = 545 nm), a broad excitation band was observed in the wavelength range 305 nm–380 nm due to the f→d transition of 4f shell of Tb ion. Furthermore, emission spectra (λex = 375 nm) consist of bands at 489 nm, 545 nm, 585 nm and 623 nm due to the transitions at 5D4 → 7F6,5,4, and 3, respectively with doping. For an optimum doping concentration with x = 0.12, a high intensity green emission line at 545 nm came out as 5D4 → 7F5 dominating transition of terbium ion. Hence, the results explore the application of Gd2Ti2O7 composition as Tb-fluorescence with the optimum doping concentration of 6%.