Porous hollow carbon spheres (PHCSs) are prepared through hydrothermal carbonization of alginic acid and subsequent chemical activation by KOH. The porosity of the alginic acid derived PHCSs can be finely modulated by varying activation temperature in the range of 600–900 °C. The PHCSs activated at 900 °C possess the largest specific surface area (2421 m2 g−1), well-balanced micro- and mesoporosity, as well as high content of oxygen-containing functional groups. As the electrode material for supercapacitors, the PHCSs exhibit superior capacitive performance with specific capacitance of 314 F g−1 at current density of 1 A g−1. Pt nanodendrites supported on the PHCSs are synthesized by polyol reduction method which exhibit high electrocatalytic activity towards methanol oxidation reaction (MOR). Moreover, CO-poisoning tolerance of the Pt nanodendrites is greatly enhanced owing to the surface chemical property of the PHCSs support.