Developing Pd catalysts with high catalytic activity and stability for formic acid dehydrogenation still remains a great challenge. Herein, a nitrogen/amino-cofunctionalized MWCNTs-supported Pd catalyst (Pd/MWCNTs-AP) was prepared in solution by a green, mild, and fast plasma technology. At 333 K reaction temperature, the turnover frequency (8415 h−1) over Pd/MWCNTs-AP for formic acid dehydrogenation was 1.26 and 5.16 times of those using Sigma-Aldrich Pd/C and thermal reduction prepared Pd/MWCNTs-AH, respectively. Impressively, the activity of Pd/MWCNTs-AP was not reduced during the six reaction cycles. In contrast, after the sixth cycle, the volume of gas produced using Sigma-Aldrich Pd/C decreased to 48 % of the initial volume. The results of structural characterization showed that Pd/MWCNTs-AP possessed ultrasmall-sized Pd, high Pd/C and N/C atomic ratios, and abundant –OH, facilitating the breakage of C–H and O–H bonds in formic acid to produce H and thus H2. Therefore, Pd/MWCNTs-AP exhibited excellent catalytic performance for formic acid dehydrogenation.