A new hyperbranched polyamidoamine polymer functionalized with cucurbituril (HBPA@Cucurbituril) was fabricated to enhance the antifouling properties of polyethersulfone (PES) membrane to remove dye pollutants and heavy metal ions (e.g., As3+ and Hg2+). ATR-FTIR, TGA, SEM, zeta potential, AFM, water contact angle (WCA), and SEM analyses were used to investigate the morphology of modified membranes. The WCA evaluations indicated that the 0.5wt% HBPA@cucurbituril membranes showed the best hydrophilicity improvement compared to the bare membrane (decrement from 66.6° to 37.9°). In the best case, the optimally modified membrane (0.5wt%) indicated the best permeability (8.5L/m2.h.bar), fouling resistance (flux recovery ratio of 92.42%), dye rejection (Direct Red 16: 98.7%, Reactive Blue 19: 99.8%, Crystal Violet: 97.3% and Methylene Blue: 98.4%) and heavy metal removal of (As3+: 99.7% and Hg2+: 99.2%). This study offers a clear perspective on the treatment of industrial effluents.