Palladium-catalyzed cross-couplings have played an increasingly important role in the synthesis of agrochemicals. In this review, the applications of palladium-catalyzed Heck reaction, Suzuki-Miyaura cross-coupling, Sonogashira coupling, Negishi cross-coupling, carbonylation, and Buchwald-Hartwig amination, in the synthesis of agrochemicals are summarized with particular emphasis on catalyst system and catalytic efficiencies. In addition, strategies and advances on ligand development in achieving high TONs for palladium-catalyzed cross-couplings applicable in agrochemical industry are discussed.