A facile soft-template method to synthesize Pd hollow nanospheres (PHNs) through a one-pot route in the presence of rhodamine B (RB) at room temperature is demonstrated. RB-PdCl42− complex formed by an electrostatic interaction is used as sacrificial template, which can self-degrade to synthesize metal hollow nanostructures. The PdCl42− ions are continually reduced in situ and the hollow nanostructures form gradually. The as-prepared PHNs are characterized by transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical measurements. The as-prepared PHNs exhibit enhanced catalytic activity and durability as electrocatalysts for direct methanol fuel cells and direct formic acid fuel cells.