Concrete, due to its low cost, durability and fire resistance, is one of the world’s most widely used construction materials. Concrete is typically reinforced with steel bars and welded wire mesh. Since the cost of steel is increasing and steel corrosion is a significant contributor to structural failure, it is advantageous to find an alternative replacement reinforcement material which can not only replace the steel, but also resist corrosion. Over the past few decades, polymeric fibres have been used as concrete reinforcement. The chemical bond between the polymeric fibre and the cementitious matrix is an important factor in the fibre’s performance as a concrete reinforcement. Despite the great importance of the chemical bonding at the polymeric fibre/concrete interface, the chemical bonding at the interface is not well understood. To investigate the chemical interactions between polymeric materials and concrete, model systems of polymeric powder/white cement and polymeric fibre/white cement were chosen, where white cement was chosen for its suitability for nuclear magnetic resonance (NMR) experiments. The chemical interactions between poly(ethylenevinyl acetate) (EVA), poly(ether imide) (PEI), and poly(vinylidene fluoride) (PVDF) polymeric powders were studied via 13C NMR spectroscopy. It was found that EVA admixture undergoes hydrolysis in a cementitious matrix and follows a pseudo-second order kinetics model up to 32 days of cement hydration. PEI was also found to undergo hydrolysis at the imide functional group in a cementitious matrix. PVDF powder undergoes dehydrofluorination in the cementitious environment, producing a brown coloured polymer which is a result of conjugation of the polymer backbone. The interfacial transition zone between fluoropolymeric powder/white cement and steel and polymeric fibres (high density polyethylene/polypropylene, poly(vinyl alcohol), PEI, PVDF, and Nylon 6.6) was studied at short range using 19F, 27Al, and 43Ca NMR spectroscopy and at long range using the scanning electron microscopy/energy dispersive spectroscopy method. It was concluded that the chemistry of polymeric fibres themselves can alter the surrounding interfacial transition zone such that the calcium silicate hydrate favours a tobermorite or jennite-like structure, which could contribute to a strong or weak interface.