Assessment of soil contamination and its long-term monitoring are necessary to evaluate the effectiveness of phytoremediation systems. Spectral sensing-based monitoring methods promise obvious benefits compared to field-based methods: lower cost, faster data acquisition and better spatio-temporal monitoring. This paper reviews the theoretical basis whereby proximal spectral sensing of soil and vegetation could be used to monitor phytoremediation of metal-contaminated soils, and the eventual upscaling to imaging sensing. Both laboratory and field spectroscopy have been applied to sense heavy metals in soils indirectly via their intercorrelations with soil constituents, and also through metal-induced vegetation stress. In soil, most predictions are based on intercorrelations of metals with spectrally-active soil constituents viz., Fe-oxides, organic carbon, and clays. Spectral variations in metal-stressed plants is particularly associated with changes in chlorophyll, other pigments, and cell structure, all of which can be investigated by vegetation indices and red edge position shifts. Key shortcomings in obtaining satisfactory calibration for monitoring the metals in soils or metal-related plant stress include: reduced prediction accuracy compared to chemical methods, complexity of spectra, no unique spectral features associated with metal-related plant stresses, and transfer of calibrations from laboratory to field to regional scale. Nonetheless, spectral sensing promises to be a time saving, non-destructive and cost-effective option for long-term monitoring especially over large phytoremediation areas, and it is well-suited to phytoremediation networks where monitoring is an integral part.