In addition to single-angle reflectance data, multi-angular observations can be used as an additional information source for the retrieval of properties of an observed target surface. In this paper, we studied the potential of multi-angular reflectance data for the improvement of leaf area index (LAI) and leaf chlorophyll content (LCC) estimation by numerical inversion of the PROSAIL model. The potential for improvement of LAI and LCC was evaluated for both measured data and simulated data. The measured data was collected on 19 July 2016 by a frame-camera mounted on an unmanned aerial vehicle (UAV) over a potato field, where eight experimental plots of 30 × 30 m were designed with different fertilization levels. Dozens of viewing angles, covering the hemisphere up to around 30° from nadir, were obtained by a large forward and sideways overlap of collected images. Simultaneously to the UAV flight, in situ measurements of LAI and LCC were performed. Inversion of the PROSAIL model was done based on nadir data and based on multi-angular data collected by the UAV. Inversion based on the multi-angular data performed slightly better than inversion based on nadir data, indicated by the decrease in RMSE from 0.70 to 0.65 m2/m2 for the estimation of LAI, and from 17.35 to 17.29 μg/cm2 for the estimation of LCC, when nadir data were used and when multi-angular data were used, respectively. In addition to inversions based on measured data, we simulated several datasets at different multi-angular configurations and compared the accuracy of the inversions of these datasets with the inversion based on data simulated at nadir position. In general, the results based on simulated (synthetic) data indicated that when more viewing angles, more well distributed viewing angles, and viewing angles up to larger zenith angles were available for inversion, the most accurate estimations were obtained. Interestingly, when using spectra simulated at multi-angular sampling configurations as were captured by the UAV platform (view zenith angles up to 30°), already a huge improvement could be obtained when compared to solely using spectra simulated at nadir position. The results of this study show that the estimation of LAI and LCC by numerical inversion of the PROSAIL model can be improved when multi-angular observations are introduced. However, for the potato crop, PROSAIL inversion for measured data only showed moderate accuracy and slight improvements.