Carbon microspheres were prepared by microwave-assisted hydrothermal treatment, at 180 °C, of commercial carbohydrates (saccharose, glucose, and xylose) and xylose extract obtained from almond shells with varying synthesis parameters. When 1.6 M aqueous solutions of commercial carbohydrates were used, 2–10 μm carbon microspheres were obtained from saccharose after 15 min, while a longer amount of time (60 min) and the addition of acid medium (1% v/v H2SO4, 1% v/v H3PO4) were needed to obtain carbon microspheres from commercial xylose and glucose (≤ 1 μm). The higher reactivity of saccharose could be related to the formation, during heating, of fructose, which is more reactive than glucose and xylose. An increase in the acid concentration and in the carbohydrate concentration increased the formation and size of the microspheres. Comparative experiments with conventional heating did not produce a solid. Interestingly, when xylose extract obtained from almond shells was used, small carbon microspheres (1–3 μm) were obtained at a much lower concentration (0.2 M) and time (15 min) than with commercial xylose. This could be related to the acid medium used during extraction of xylose from the biomass. Activation of microspheres with CO2 resulted in high-surface area materials (243–326 m2/g) with great potential as catalytic supports.