Sun-induced chlorophyll fluorescence (F) is a novel remote sensing parameter providing an estimate of actual photosynthetic rates. A combination of this new observable and Monteith’s light use efficiency (LUE) concept was suggested for an advanced modeling of gross primary productivity (GPP). In this demonstration study, we evaluate the potential of both F and the more commonly used photochemical reflectance index (PRI) to approximate the LUE term in Monteith’s equation and eventually improve the forward modeling of GPP diurnals. Both F and the PRI were derived from ground and airborne based spectrometer measurements over two different crops. We demonstrate that approximating dynamic changes of LUE using F and PRI significantly improves the forward modeling of GPP diurnals. Especially in sugar beet, a changing photosynthetic efficiency during the day was traceable with F and incorporating F in the forward modeling significantly improved the estimation of GPP. Airborne data were projected to produce F and PRI maps for winter wheat and sugar beet fields over the course of one day. We detected a significant variability of both, F and the PRI within one field and particularly between fields. The variability of F and PRI was higher in sugar beet, which also showed a physiological down-regulation of leaf photosynthesis. Our results underline the potential of F to serve as a superior indicator for the actual efficiency of the photosynthetic machinery, which is linked to physiological responses of vegetation.