The main properties of chars produced from corn stover, either by pyrolysis at 550°C (to produce biochar) or by hydrothermal carbonisation (to produce hydrochar), were studied. Carbonaceous materials were characterised by: SEM imaging, solid-state 13C NMR, FT-IR, Raman spectroscopy, and XPS. The following parameters were determined: elemental composition, cation exchange capacity, acid groups contents, BET, and yield. The hydrochar had a low ash content and low pH (4.7); recovery of C was high (57%), although only about half of the C was aromatic. Atomic O/C and H/C ratios in the hydrochar were higher than in the biochar. The same pattern was observed for the estimated concentration of carboxylic functional groups (0.07 compared with 0.04 mol/kg). The biochar had higher ash content than the hydrochar, and also higher pH (~10) (lime equivalence ~40 kg CaCO3/t). The C recovery (46%) was lower than in the hydrochar, although most of the C recovered was aromatic. Both chars could be used as soil amendments, for very different requirements. Soil responses and the residence times of the chars (especially the hydrochar) must be studied in detail to pursue long-term C sequestration.