Poly(ionic liquid)s (PILs) are polymers containing ions in their side-chain or backbone, and the designability and outstanding physicochemical properties of PILs have attracted widespread attention from researchers. PILs have specific characteristics, including negligible vapor pressure, high thermal and chemical stability, non-flammability, and self-assembly capabilities. PILs can be well combined with advanced analytical instruments and technology and have made outstanding contributions to the development of biomedicine aiding in the continuous advancement of science and technology. Here we reviewed the advances of PILs in the biomedical field in the past five years with a focus on applications in proteomics, drug delivery, and development. This paper aims to engage pharmaceutical and biomedical scientists to full understand PILs and accelerate the progress from laboratory research to industrialization.