Diversity-oriented strategies can facilitate the rapid exploration of chemical space during small-molecule synthesis, but similar approaches are underutilized for macromolecular substrates. Expanding the repertoire of soft material manipulations to accommodate iterative diversifications could enable the design of bespoke polymers with a range of novel structures and properties. To explore this concept, we chose to leverage the efficiency of Suzuki-Miyaura cross-coupling to rapidly access an array of functionalized polystyrene surrogates from a readily accessible polystyrene-p-pinacol boronic ester. A variety of C(sp(2)) electrophiles efficiently coupled with our model polymer (51-99% functionalization) in moderate-to-good yields (44-96%). Optimized coupling reactions afforded products with minimal changes in overall dispersity (as determined by gel permeation chromatography), which suggested that the desired coupling occurred with good fidelity. Select products were subjected to further modifications (e.g., Wittig olefination, reduction, imine condensation) to showcase the diverse array of reactivities that can be accessed using our strategy.