Cross-linked poly(N-isopropylacrylamide)-based polymer containing palladium species (PNIPAAm-Pd) was prepared. PNIPAAm-Pd showed high catalytic activity in Mizoroki-Heck and Suzuki-Miyaura reactions. An increase in affinity of PNIPAAm-Pd for organic substrates at higher temperatures than LCST (lower critical solution temperature) led to an acceleration of the reactivity and loss of affinity at lower temperatures than LCST allowed easy separation of organic products upon completion of the reaction. In addition, the recovered catalyst could also be used for consecutive reactions without any significant loss of catalytic efficacy.