In order to investigate the potential of various olive cultivars and leaf sampling times for phytochemical farming practice in Croatia, phenolic and mineral composition was determined in olive leaves of four Croatian cultivars and Italian cultivar Leccino collected at three occasions, in October 2017, January 2018, and March 2018. Istarska bjelica turned out to have the largest phytochemical potential among the investigated cultivars due to steady high oleuropein concentrations found in its leaves. The concentration of main phenolic components in Istarska bjelica leaves changed only slightly during the sampling period, suggesting the possibility of its higher capability for low air temperatures stress resistance and different metabolic response compared to the other studied cultivars. Low air temperatures increased the oleuropein level and antioxidant activity in leaves of Leccino, Oblica, Levantinka, and Drobnica cultivars, which may be of crucial phytochemical farming interest. Each of the investigated olive cultivars was characterized by a specific leaf mineral nutrient composition, which could have had a specific role in their interplay with phenols.