This study presents a facile and general method for fabrication of carbon spheres with tunable morphologies based on the sol gel reaction of a novel polymeric carbon precursor. The carbon precursor was fabricated by the synthesis of resole, a low-molecular weight polymer of phenol and formaldehyde, and then the modification with poly(ethylene glycol) monomethyl ether (PEG). By turning the modification degree of resole with different amounts of PEG and the hydrolysis and condensation reactions of this precursor, carbon spheres with various morphologies, including regular spheres, hollow spheres of different pore sizes, and raspberry- and peanut-like spheres, were produced easily. This should be attributed to the condensation, self-assembly, and phase separation of the new polymeric carbon precursors during the sol-gel process.