A poly(ionic liquid) (PIL) obtained by polymerizing an ionic liquid (IL) monomer exhibits the characteristics of low cost and good biocompatibility, and it retains the excellent properties of the monomer. However, there is still a need to develop PILs for biomedical applications, which has been paid little attention. Herein, an amphiphilic block polymer containing a PIL block is synthesized, which simultaneously includes a targeted ligand, a photo-responsive block, and a pH-responsive block. The resultant amphiphilic block polymer can self-assemble into drug-loaded nanoparticles with a size of ∼80 nm in aqueous solution, and its drug loading capacity is as high as 70%. Moreover, the drug releasing mechanism of these drug-loaded nanoparticles can be triggered by light and pH stimuli. These novel amphiphilic PIL-based drug-loaded nanoparticles show highly effective antitumor effects, providing a promising approach for the delivery and controlled release of chemotherapy drugs in cancer therapy.