The gadolinium vanadate doped with samarium (GdVO4:Sm3+) nanopowder was prepared by the solution combustion synthesis (SCS) method. After synthesis, in order to achieve full crystallinity, the material was annealed in air atmosphere at 900 °C. Phase identification in the post-annealed powder samples was performed by X-ray diffraction, and morphology was investigated by high-resolution scanning electron microscope (SEM) and transmission electron microscope (TEM). Photoluminescence characterization of emission spectrum and time resolved analysis was performed using tunable laser optical parametric oscillator excitation and streak camera. In addition to samarium emission bands, a weak broad luminescence emission band of host VO43− was also observed by the detection system. In our earlier work, we analyzed the possibility of using the host luminescence for two-color temperature sensing, improving the method by introducing the temporal dependence in line intensity ratio measurements. Here, we showed that further improvements are possible by using the machine learning approach. To facilitate the initial data assessment, we incorporated Principal Component Analysis (PCA), t-Distributed Stochastic Neighbor Embedding (t-SNE) and Uniform Manifold Approximation and Projection (UMAP) clustering of GdVO4:Sm3+ spectra at various temperatures. Good predictions of temperature were obtained using deep neural networks. Performance of the deep learning network was enhanced by data augmentation technique.