A novel type of supramolecular nanoparticle (SNP) was self-assembled based on the balance of forces including attractive supramolecular host–guest interactions and repulsive electrostatic interactions between the host and the guest polymers. b-cyclodextrin (CD) grafted positively charged or neutral poly(glycerol methacrylate) (P+CD or PCD) and negatively charged CD-modified poly(acrylic acid) (PAA– CD) were synthesized respectively as the host polymers. While 4-tert-butylphenyl group (TBP) grafted positive poly(glycerol methacrylate) (P+TBP) was synthesized as the guest polymer to study the influencen of electrostatics in the host guest systems between CD and TBP. The resulting P+CD/P+TBP SNPs, possessing good stability, will provide a guide for the future construction of SNPs and promote the development of SNPs as carriers for biomedical applications such as drug delivery agents.