Supported Pd catalysts has found wide applications in reductive etherification of aldehydes. However, the synthesis of furfural-derived ethers on Pd catalysts has encountered great challenges because several side reactions such as over-hydrogenation of furan ring and decarbonylation always occur simultaneously under the reaction conditions. We herein reported the catalytic performance of Pd nanoparticles (∼4 nm) supported on the external surface of layered structured PLS-3 zeolite with narrow pore size (<0.4 nm) and large external surface area (80–100 m2/g). The PLS-3 with Si/Al of 92 having total acid sites of 93 μmol/g showed satisfied ether selectivity. Pd nanoparticles located on the external surface showed better etherification selectivity than those confined in the framework, due to the less diffusion limitation of furfural acetal as an intermediate.