Optical thermometry is a growing technological field which exploits the ability of certain materials to change their optical properties with temperature. In this work, poly(glycerol dendrimer) microspheres (PGLyD) encapsulating cobalt-doped hopeite (CoHo) was synthesized for its potential use as optical thermometer. The structure of the CoHo:PGLyD was studied using scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). On the basis of SEM images, the CoHo:PGLyD exhibited a spherical shape in which around 80% of the microspheres were within 0.82 µm. A multilayer feed-forward artificial neural network (MLP-ANN) was used to extract the chromaticity profile dependence of the CoHo:PGLyD with temperature. A color change was observed for the CoHo:PGLyD, going from dark blue (490-550 nm) to pale pink (650 nm) when the temperature changed from 20-200 °C, respectively. These results suggest that CoHo:PGLyD is a promising material for temperature sensing applications.