Biochar from agricultural biomasses and solid wastes represents a win-win solution for a rational waste management. Its sustainable usage requires the identification and standardization of biochar characteristics. The aim of this work was to identify the physical-chemical and spatial characteristics of biochars from pruning residues (PR), poultry litter (PL), and anaerobic cattle digestate (CD) at two pyrolysis temperatures (350 °C and 550 °C). The biochar characterization was carried out by applying emerging imaging techniques, 2D automated optical image analysis and hyperspectral enhanced dark-field microscopy (EDFM), and by SEM analysis. As predictable, the feedstock composition and the pyrolysis temperature strongly influence the physical structures of the biochar samples. Irrespective of charring temperature, PR biochar was mainly characterized by a broken and fragmented structure with an irregular and rough particle surface, completely different from the original PR wood cell. The EDFM imaging analysis evidenced the thermal degradation of PR vegetal products, composed primarily of hemicellulose, cellulose and lignin. On the contrary, small and regular particles with a smooth surface were produced by the PL pyrolysis, especially at 550 °C, due to the lower PL morphological homogeneity in comparison with the other biomasses. Finally, CD charring at both temperatures was characterized by changes in chemical composition, suggested by a lower pixel intensity. In conclusion, the emerging imaging techniques used in this study proved to be very effective in analyzing some properties of biochars, and can, therefore be considered as promising experimental strategies for detecting the feedstock and pyrolysis temperature of biochar.