Erbium (Er3+)–ytterbium (Yb3+) doped gadolinium oxysulphide (Gd2O2S) phosphor has been developed via a facile method of solid-state flux fusion, and offers two-fold spectrum modification with highly intense Stokes and anti-Stokes shift. The effect of the firing cycle on the photoluminescent response and morphology of Gd2O2S:Er,Yb is scrutinized, wherein the firing temperature was varied (1000 °C–1250 °C), keeping firing time and all other parameters constant. Interestingly, the nanostructures fired below 1150 °C showed nanorods of diameter ~200 nm and length ~1–2 µm, whereas firing at 1150 °C and above rendered nanospheres with small diameter, ~350 nm. Highly bright upconversion (UC) emission was achieved even under an extremely low excitation power density of 800 µW cm−2 from a 980 nm laser, and was comfortably visible to the naked eye. The incident power dependent studies disclosed increase in UC-emission intensity with increasing excitation power and a quasi-linear dependence on excitation power density. Intense characteristic UC-emission of Er3+ excited states at 525 nm, 556 nm and 668 nm were observed, and the green emission band was found to be dominant over the red band in intensity. Concurrently, downconversion (DC) emission at 556 nm and 669 nm was also exhibited under ultraviolet excitation (285 nm and 380 nm), with the red band being more powerful than the green, unlike UC-emission. Firing temperature dependent studies divulged the dependence of luminescence intensity on the firing cycle of the luminophore and formation of the respective luminescent phase. The UC-emission intensity was found to be maximum for samples fired at 1150 °C, whereas samples fired at 1000 °C showed the highest DC-emission intensity. The excitation and emission profile of single Gd2O2S:Er,Yb phosphor lying in the desired spectral region and as a dual spectral converter marks its possible application for enhanced harvesting of sunlight.