Smart farming techniques can be used to maximize food production. This can be achieved by the rapid detection of variations in crops and clever use of resources such as water and fertilizers, which might minimize crop stress through direct target practices. In an orchard located in the West region of Portugal (GPS coordinates 39°23′28.997″ N; 9°4′52.483″ W), a Ca biofortification workflow with seven foliar sprays of CaCl2 (4 kg ha−1 and 8 kg ha−1) was used to increase Ca contents in “Rocha” pear trees. During the biofortification process, an Unmanned Aerial Vehicle, synchronized by GPS, was used to characterize the orchard regarding its morphology (slope) and to monitor trees (NDVI—Normalized Difference Vegetation Index). These data were correlated with Ca content (assessed by X-ray fluorescence analysis) and photoassimilate synthesis (assessed by leaf gas exchange measurements). The orchard showed no major slopes and after four sprays with CaCl2, NDVI values revealed no major differences between the control and sprayed trees. Accordingly, leaf gas exchange parameters did not reveal negative impacts in the photoassimilate synthesis of the sprayed trees, although in the leaves Ca content significantly increased. The use of precision agriculture techniques in correlation with other analyses to assess plant stress is discussed.