At present, Pd containing (10-40 wt%) multiwall carbon nanotube (MWCNT) supported Pd monometallic, Pd:Au bimetallic, and PdAuCo trimetallic catalysts are prepared via NaBH4 reduction method to examine their formic acid electrooxidation activities and direct formic acid fuel cell performances (DFAFCs) when used as anode catalysts. These catalysts are characterized by advanced analytical techniques as N-2 adsorption and desorption, XRD, SAXS, SEM-EDX, and TEM. Electronic state of Pd changes by the addition of Au and Co. Moreover, formic acid electrooxidation activities of these catalysts measured by CV indicates that particle size changes in wide range play a major role in the formic acid electrochemical oxidation activity, ascribed the strong structure sensitivity of formic acid electrooxidation reaction. PdAuCo (80:10:10)/MWCNT catalyst displays the most significant current density increase. On the other hand, lower CO stripping peak potential obtained for PdAuCo (80:10:10)/MWCNT catalyst, attributed to the awakening of the Pd-adsorbate bond strength down to its optimum value, which favors higher electrochemical activity. DFAFCs performance tests and exergy analysis reveal that fuel cell performances increase with the addition of Au and Co which can be attributed to synergetic effect. Furthermore, temperature strongly influences the performance of formic acid fuel cell. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.