Diblock copolymers of poly(N-vinylpyrrolidinone) (PNVP) and poly(isoprene) (PIp) were employed as building blocks for the construction of complex cross-linked networks that present surfaces having amphiphilic character, imparted by covalent trapping of compositionally heterogeneous phase-separated morphologies. The kinetics for the homopolymerization of N-vinylpyrrolidinone by reversible addition-fragmentation chain transfer (RAFT) techniques wits studied, and the initially obtained PNVP-based macro-RAFT agents were then extended to PNVP-b-PIp block copolymers. Therefore, the PNVP chain length was held constant at a number-averaged degree of polymerization of 120. while the PIp chain length was varied to afford a series of three PNVP120-b-PIp(x) block copolymers (where x = 710, 53, and 25). These materials were then cross-linked individually using sulfur monochloride, to produce complex amphiphilic networks. The nanoscopically resolved topographies of these films were analyzed using atomic force microscopy, and their compositional heterogeneities were probed by X-ray photoelectron spectroscopy and internal reflectance infrared imaging techniques. Additionally, the surfaces were analyzed to determine the extent of surface reorganization under aqueous conditions.