A series of resorcinol/formaldehyde (RF) resin-derived carbon spheres modified by polyethylene glycol (PEG) were prepared. The effects of PEG addition time during hydrothermal treatment and molecular weight on the pore structure, surface acidic groups, particle size, and adsorption performances of the obtained spherical activated carbons were investigated. Two types of model fuel containing indole, quinoline, and dibenzothiophene (DBT) as target adsorbates were prepared to evaluate the adsorption performances of the spheres, which increased in the order of DBT