The structural orientation of an amphiphilic crystalline polymer to a highly ordered microphase-separated lamellar structure on a hydrophobic surface is presented. It is formed by the surface graft polymerization of poly(ethylene glycol)behenyl ether methacrylate onto poly(trimethylsilyl) propyne in the presence of allylamine. In particular, allylamine plays a pivotal role in controlling the crystalline phase, configuration, and permeation properties. The resulting materials are effectively used to improve the CO capture property of membranes. Upon the optimization of the reaction conditions, a high CO permeability of 501 Barrer and a CO /N ideal selectivity of 77.2 are obtained, which exceed the Robeson upper bound limit. It is inspiring to surpass the upper bound limit via a simple surface modification method.