The ability to precisely monitor soil moisture is highly valuable in industries including agriculture and civil engineering. As soil moisture is a spatially erratic and temporally dynamic variable, rapid, cost-effective, widely applicable, and practical techniques are required for monitoring soil moisture at all scales. If a consistent numerical relationship between soil moisture content and soil reflectance can be identified, then soil spectroscopic models may be used to efficiently predict soil moisture content from proximal soil reflectance and/or remotely sensed data. Previous studies have identified a general decrease in visible–NIR soil reflectance as soil moisture content increases, however, the strength, best wavelengths for modelling, and domain of the relationship remain unclear from the current literature. After reviewing the relevant literature and the molecular interactions between water and light in the visible–NIR (400–2500 nm) range, this review presents new analyses and interprets new 1 nm resolution soil reflectance data, collected at >20 moisture levels for ten soil samples. These data are compared to the results of other published studies, extending these as required for further interpretation. Analyses of this new high-resolution dataset demonstrate that linear models are sufficient to characterise the relationship between soil moisture and reflectance in many cases, but relationships are typically exponential. Equations generalising the relationship between soil MC and reflectance are presented for a number of wavelength ranges and combinations. Guidance for the adjustment of these equations to suit other soil types is also provided, to allow others to apply the solutions presented here and to predict soil moisture content in a much wider range of soils.