Gas evolution during electrochemical deposition has long been regarded as undesired and deliberately suppressed. Here, we show a new role of electrochemically evolved hydrogen bubbles, serving as both templates and reducing agent to form hollow Au nanoparticles via electroless deposition. Hollow gold nanoparticles with a complete nanocrystalline shell and a 50 nm hollow core were fabricated. By controlling the shell thickness, particle size can be varied from 100 to 150 nm. The process is very simple, scalable, and with a high throughput. Using this method, more complicated hollow nanostructures such as double nanoshells ("nanomatryoshka") can also be synthesized. These hollow nanoparticles possess desirable plasmonic properties and can potentially be used as nanocontainers to store and deliver gaseous materials. In addition, the process can be used for fundamental studies of nanobubble formation mechanism.