We propose a synthesis method for hollow copolymer nanoparticles, in which the size is controllable by the wettability of the materials designed by relative energy difference (RED). We investigated the influence of cross-linkers in RED and the hollow polymer nanoparticle synthesis. The size of the nanoparticles was characterized by scanning electron microscopy and transmission electron microscopy images. The diameter size of the hollow copolymer (styrene-co-methyl methacrylate) changes from 400 to 141 nm and the average core-vacancy sizes changes from 330 to 71 nm as increasing the feed ratio of the cross-linker, divinyl benzene, from 0.07 to 0.43. Cross-linkers in polymerization precipitates a polymerization reaction to produce seed copolymer particles quickly. The seed copolymer is a more transferrable medium through the surfactants across emulsion droplets and inhibits emulsion growth by unstable concentration variations of seed copolymers in emulsions. Therefore, Ostwald ripening was reduced by a higher feeding ratio of the cross-linker in the copolymer, which tends to produce smaller sized hollow nanoparticles.