Palladium (Pd) nanoparticle catalysis has attracted increasing attention due to its efficient catalytic activity and its wide application in environmental protection and chemical synthesis. In this work, Pd nanoparticles (about 71 nm) were synthesized in aqueous solution by microwave-assisted thermal synthesis and immobilized in beech wood blocks as Pd@wood catalysts. The wood blocks were first hydrothermally treated with 10% NaOH solution to improve the internal structure and increase their porosity, thereby providing favorable attachment sites for the formed Pd nanoparticles. The stable deposition of Pd nanoparticle clusters on the internal channels of the wood blocks can be clearly observed. In addition, the catalytic performance of the prepared Pd@wood was investigated through two model reactions: the reduction of 4-nitrophenol and Cr(VI). The Pd@wood catalyst showed 95.4 g−1 s−1 M−1 of normalized rate constant knorm and 2.03 min−1 of the TOF, respectively. Furthermore, Pd nanoparticles are integrated into the internal structure of wood blocks by microwave-assisted thermal synthesis, which is an effective method for wood functionalization. It benefits metal nanoparticle catalysis in the synthesis of fine chemicals as well as in industrial wastewater treatment.