Leaf water potential (LWP) is an important indicator of plant water status. However, its determination via classical pressure-chamber measurements is tedious and time-consuming. Moreover, such methods cannot easily account for rapid changes in this parameter arising from changes in environmental conditions. Spectrometric measurements, by contrast, have the potential for fast and non-destructive measurements of plant water status, but are not unproblematic. Spectral characteristics of plants vary across plant development stages and are also influenced by environmental factors. Thus, it remains unclear whether changes in leaf water potential per se can reliably be detected spectrometrically or whether such measurements also reflect autocorrelated changes in the leaf water content (LWC) or the aerial plant biomass. We tested the accuracy of spectrometric measurements in this context under controlled climate chamber conditions in series of six experiments that minimised perturbing influences but allowed for significant changes in the LWP. Short-term exposure of dense stands of plants to increasing or decreasing artificial light intensities in a growth chamber more markedly decreased LWP than LWC in both wheat and maize. Significant relationships (R2-values 0.74-0.92) between LWP and new spectral indices ((R940/R960)/NDVI; R940/R960) were detected with or without significant changes in LWC of both crop species. The exact relationships found, however, were influenced strongly by the date of measurement or water stress induced. Thus, global spectral relationships measuring LWP probably cannot be established across plant development stages. Even so, spectrometric measurements supplemented by a reduced calibration dataset from pressure chamber measurements might still prove to be a fast and accurate method for screening large numbers of diverse lines.