Cemented paste backfill (CPB) comprising mineral tailings, binders and mixing waters is an important potential support material in the mining industry. As the mechanical properties of CPB are significantly influenced by its microstructural characteristics the development of measurement tools to better understand its pore structure evolution is important for its increased utilisation. This study reports the application of low-field nuclear magnetic resonance (NMR) relaxation time measurements to characterise the microstructural evolution of CPB materials over 56 days of hydration, contrasting common tap water and hypersaline water (~22 wt% salt) as mixing waters. Distinct NMR relaxation time populations were evidenced within each CBP sample, revealing the presence of both capillary (T1,2 ≈ 10 ms) and gel pore water (T1,2 ≈ 300 – 500 µs), with time-dependent relaxation measurements facilitating characterisation of capillary pore structure evolution over the hydration period assessed. Hypersaline samples demonstrated a time-lag in this measured capillary pore evolution, relative to those hydrated with tap water, while hydration rates were observed to increase with increased CPB binder content. Further, both T1 and T2 NMR relaxation times were found to correlate with the uniaxial compressive strength of the CPB materials investigated, facilitating the formulation of a predictive correlation function between NMR relaxation characteristics and mechanical properties.