Adhesion to chemically inert materials (CIM) through non-covalent interactions without surface modifications represents a formidable challenge in adhesion science. We report herein a rigid poly(acrylamide) bearing multiple benzene rings in its side chains that can strongly adhere to the chemically inert surface of the polyolefin without the need for surface modifications. This adhesive is rationally designed based on our previous findings. The adhesion to polyolefin is triggered by the formation of multiple CH/p < /span> interactions at the macroscopic interface. The adhesion strength is far greater than that of adhesions using surface modifications or commercially available polyolefin adhesives. In this study, the adhesion mechanism is carefully analyzed by experimental and theoretical studies. We anticipate that this study could address the long-standing issue of achieving strong adhesion to CIMs without requiring surface modifications and pave the way for future research into the development of new adhesives for CIMs.