Eu3+ doped GdPO4 orthophosphates with hexagonal and monoclinic crystal structures were prepared by a solvothermal process at 160 °C. Nanoparticles (NPs) and nanowires (NWs) were obtained using a mixture of water and glycerol as solvents. Luminescence properties of 5% Eu3+ doped GdPO4 NPs and NWs were investigated. As-obtained luminescent NWs:Eu and NPs:Eu powders were post-annealed at 750 °C since this temperature did not change neither their initial morphology nor their crystalline structure and led to luminescence efficiency intense enough to suit optical applications. A post-heating treatment of the samples at higher temperature (1000 °C) resulted in a change in both the crystalline structure from hexagonal to monoclinic form and the morphology. Excitation and emission spectra as well as luminescence decays were recorded on both post-annealed luminescent NW:Eu and NP:Eu powders. A comparative study of the optical results obtained for the different morphologies and structures was carried out by calculating the asymmetry ratio (A21) of Eu3+ from emission spectra. The symmetry of the local environment of Eu3+ activators has been described in the frame of Judd–Ofelt theory, using Ω2 and Ω4 intensity parameters derived from emission spectra data analysis, adopting a standard procedure. It was observed that Ω2 value for the NPs is different from that of the NWs indicating that the environment surrounding the active ion changes depending on the sample morphologies. The radiative lifetimes of the 5D0 excited state and the corresponding branching ratios for different emission transitions were also estimated and compared to the recorded luminescence decay rates at room temperature.