Zeolite Y nanosheets with a micro-meso-macroporous structure were synthesized, and applied in the assembly of a Pd catalyst (Pd/NS-Y) for direct vinylation of thiophenes with high activity and selectivity, as compared to Pd(OAc)2, Pd(NO3)2, and Pd(PPh3)4 catalysts. This feature should be assigned to the highly dispersed Pd(δ+) (δ < 2) species in Pd/NS-Y, which are more active than Pd(2+).