In this work, a different polymer chain structure was synthesized to study π-π interactions between polymer and reduced graphene oxide (RGO). Polymers with different chain structures were obtained from free radical copolymerization of styrene with 4-cyanostyrene (containing substituted phenyl rings) and 2-vinylnaphthalene (containing naphthalene rings). In this work, the polystyrene, poly(styrene-co-4-cyanostyrene) and poly(styrene-co-2-vinylnaphthalene) were named as PS, PSCN and PSNP, respectively. RGO was prepared through modified Hummers’ method and further thermal reduction, and nanocomposites were prepared by solution blending. Thus, different π-π interactions were formed between polymers and RGO. Raman and thermal gravimetric analysis (TGA) were used to characterize the interfacial interaction, showing that the trend of the interfacial interaction should be in the order of RGO/PSCN, RGO/PS, and RGO/PSNP. The differential scanning calorimetry (DSC) measurement showed that, compared with polymer matrix, the glass transition temperature (T_g) of RGO/PS, RGO/PSCN and RGO/PSNP nanocomposites with the addition of 4.0 wt% RGO are increased by 14.3 °C, 25.2 °C and 4.4 °C, respectively. Compared with π-π interaction only formed through aromatic rings, substituent groups changed the densities of electron clouds on the phenyl rings. This change resulted in the formation of donor-acceptor interaction and reinforcement of the π-π interaction at the interface, which leads to increased value of T_g. This comparative study can be useful for selecting appropriate interaction groups, as well as suitable monomers, to prepare high performance nanocomposites.