Two types of facile approaches toward ultrafine Ag/polymer hybrid nanoparticles (NPs) within 10 nm are introduced. Template and in-situ formation method are developed by photoreduction based on inverse microemulsion (IME) polymerization of N,N-dimethylacrylamide (DMAA). The template method refers to the usage of size-varied polymeric PDMAA NPs as templates for the preparation of Ag/PDMAA hybrids with desired morphology and optical property. To avoid the self-seeding nucleation of free Ag+ in the solution, in-situ formation method is developed by introducing AgNO3 during IME polymerization, in which product hybrids could be obtained via autoprecipitation in large scale. Additionally, the produced Ag/PDMAA hybrids show high antibacterial performance.