In this work, hierarchical Pt4Co multi‐dendrites (MDs) with abundant active sites were synthesized by using a one‐pot solvothermal co‐reduction approach, where cetyltrimethylammonium chloride (CTAC), citric acid, and oleylamine served as the structure director, eco‐friendly reducing agent, and co‐reductant, respectively. The architectures were mainly characterized by using a series of characterization techniques, demonstrating the enlarged electrochemically active surface area of 28.27 m2 g−1, much enhanced mass activity and specific activity for oxygen reduction reaction (279.14 mA mg−1Pt and 0.89 mA cm−2) and glycerol oxidation reaction (1422.56 mA mg−1Pt, 4.58 mA cm−2) comparable with commercial Pt black, along with the superior durability. These results demonstrate the potential applications of the synthesized Pt4Co MDs catalyst in energy storage and transformation.