A facile method to boost the catalysis of Pd nanoparticulate catalysts by simple C2H2 treatment is developed. During the C2H2 treatment, Pd nanoparticles serve as active catalysts to polymerize C2H2 into transpolyacetylene. The deposition of trans-polyacetylene layer on Pd nanoparticles makes their surface hydrophobic. Such a hydrophobic surface modification helps to accumulate more hydrophobic substrates during catalysis, making the modified Pd nanoparticulate catalysts more active than untreated catalysts in the catalytic reaction involving hydrophobic substrates. Moreover, the coating of polyacetylene on Pd creates encapsulated Pd nanocatalysts, stabilizing Pd nanoparticles against sintering or aggregation. Since the catalytic polymerization of polyacetylene on Pd is not facet dependent, the development is readily applied to enhance the catalysis of commercial Pd nanoparticulate catalysts by simple C2H2 treatment.