It is an important challenge to effectively remove environmental pollutants such as polycyclic aromatic hydrocarbons (PAHs), dyes, and heavy metal ions at a low cost. Herein, we present a multifunctional homopolymer vesicle self-assembled from a scalable homopolymer, poly(amic acid) (PAA), at room temperature. The vesicle can efficiently eliminate PAHs, cationic dyes, and heavy metal ions from water based on π-π stacking, hydrophobic effect, and electrostatic interactions with the pollutants. The residual concentrations of PAHs, cationic dyes, and heavy metal ions (such as Ni) in water are lower than 0.60 and 0.30 parts per billion (ppb) and 0.095 parts per million (ppm), respectively, representing a promising adsorbent for water remediation. Furthermore, precious metal ions such as Ag can be recovered into silver nanoparticles by in situ reduction on the membrane of PAA vesicles to form a silver nanoparticle/vesicle composite (Ag@vesicle) that can effectively catalyze the reduction of toxic pollutants such as aromatic nitro-compounds and be recycled for more than ten times.