The electrochemical properties of carbonaceous materials produced by hydrothermal carbonization, referred to as hydrochar, can be substantially improved by post-carbonization via pyrolysis. Although these materials have been widely studied for a variety of applications, the mechanisms underlying the pyrolysis are yet poorly understood. This study provides a comprehensive temperature-resolved characterization of the chemical composition, morphology and crystallinity of sucrose-derived hydrochar during pyrolysis. Thermogravimetric analysis, differential scanning calorimetry, and elemental analysis have shown that the dry hydrochar loses about 41% of its dry mass due to the exothermic disintegration of oxygen-containing groups until the carbonization is completed at about 850 °C with a total carbon yield of 93%. The carbonization and aromatization of the initially furanic and keto-aliphatic structure were analyzed by 13C solid-state nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The transition from an amorphous to a nanocrystalline graphitic structure was analyzed using X-ray diffraction and Raman spectroscopy. The pore formation mechanism was examined by helium ion microscopy, transmission electron microscopy, and nitrogen adsorption measurements. The results indicate the formation of oxygen-rich nanoclusters up to 700 °C, which decompose up to 750 °C leaving behind equally sized pores, resulting in a surface area of up to 480 m2/g.