Carbon nanospheres (CNSs) prepared by hydrothermal approach and post-functionalization with alkali solutions were employed as solid base catalysts in aldol condensation. The negative charge and alkalinity of CNS surfaces were controlled by the concentration of alkali solutions, leading to the high selectivity superior to aqueous NaOH as the traditional catalyst. Furthermore, CNSs with varying surface alkalinity can be adopted as proper supports for highly dispersed Pd nanoparticles with well-controlled size distribution. The optimized alkaline CNS-supported Pd catalysts demonstrated enhanced reactivities in the solvent-free selective oxidation of benzyl alcohol and the aerobic oxidation of glycerol. In-depth characterizations of their structural and electronic properties by transmission electron microscope (TEM), field emission scanning electron microscope (FESEM), Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscopy (XPS) were performed to elucidate the nature of the active sites and the mechanism. The effect of electron density, size of Pd nanoparticles as well as the surface alkalinity of supports on the catalytic performance has been unveiled. (C) 2015 Elsevier B.V. All rights reserved.