Abstract In this work, a facile synthesis procedure was developed to deposit Pt−Pd dendrites using the chronopotentiometry (CP) method on polyaniline/carbon nanotube composites. The morphology of the bimetallic Pt−Pd dendrites exhibited a petal‐like shape. The results indicated that multi‐walled carbon nanotubes with larger diameters (approximately 60 nm) demonstrated enhanced support capabilities for achieving uniform dispersion of Pt−Pd dendrites. The electrochemical mass activity for methanol oxidation reaction (MOR) of Pt 72 Pd 28 /PANI/CNTs composites reached 670 mA mg −1 Pt+Pd , representing a 1.2‐fold increase compared to that of Pt/C. Moreover, the I f /I b value of Pt 72 Pd 28 /PANI/CNTs catalyst was 1.9 times higher than that of Pt/C catalyst. Notably, the Pt 72 Pd 28 dendrites displayed superior catalytic performance and CO ad tolerance in comparison to commercial Pt/C catalysts, as evidenced by their high mass activity and I f /I b value. These research findings present a novel approach for preparing highly active Pt−Pd binary catalysts.