Agro-industrial waste valorization is an attractive approach that offers new alternatives to deal with shrinkage and residue problems. One of these approaches is the synthesis of advanced carbon materials. Current research has shown that citrus waste, mainly orange peel, can be a precursor for the synthesis of high-quality carbon materials for chemical adsorption and energy storage applications. A recent approach to the utilization of advanced carbon materials based on lignocellulosic biomass is their use in solar absorber coatings for solar-thermal applications. This study focused on the production of biochar from Citrus aurantium orange peel by a pyrolysis process at different temperatures. Biochars were characterized by SEM, elemental analysis, TGA-DSC, FTIR, DRX, Raman, and XPS spectroscopies. Optical properties such as diffuse reflectance in the UV−VIS−NIR region was also determined. Physical-chemical characterization revealed that the pyrolysis temperature had a negative effect in yield of biochars, whereas biochars with a higher carbon content, aromaticity, thermal stability, and structural order were produced as the temperature increased. Diffuse reflectance measurements revealed that it is possible to reduce the reflectance of the material by controlling its pyrolysis temperature, producing a material with physicochemical and optical properties that could be attractive for use as a pigment in solar absorber coatings.