Nanoporous gold with networks of interconnected ligaments and highly porous structure holds stimulating technological implications in fuel cell catalysis. Current syntheses of nanoporous gold mainly revolve around de-alloying approaches that are generally limited by stringent and harsh multistep protocols. Here we develop a one-step solution phase synthesis of zero-dimensional hollow nanoporous gold nanoparticles with tunable particle size (150-1,000 nm) and ligament thickness (21-54 nm). With faster mass diffusivity, excellent specific electroactive surface area and large density of highly active surface sites, our zero-dimensional nanoporous gold nanoparticles exhibit ~1.4 times enhanced catalytic activity and improved tolerance towards carbonaceous species, demonstrating their superiority over conventional nanoporous gold sheets. Detailed mechanistic study also reveals the crucial heteroepitaxial growth of gold on the surface of silver chloride templates, implying that our synthetic protocol is generic and may be extended to the synthesis of other nanoporous metals via different templates.