Nanoparticles produced from gallium-based liquid metal alloys have been explored for developing applications in the fields of electronics, catalysis, and biomedicine. Nonetheless, physical properties, such as phase behavior at micro-/nanosize scale, are still significantly underexplored for such nanoparticles. Here, we conduct an in situ investigation of phase behavior for gallium-based liquid metal nanoparticles and discover the unprecedented coexistence of solid particles in spherical liquid metal shells without the support of a crystalline substrate. The particles can also transform into solid Janus nanoparticles after temperature cycling. In addition, we investigate the optical properties of the nanoparticles before and after phase separation using in situ electron energy-loss spectroscopy. Most importantly, we discover that increasing the content of indium within the nanoparticle can stabilize the solid-core/liquid-shell structure at room temperature. This study provides a foundation to engineer liquid metal nanoparticles for developing new applications in nanoscale optical platforms and shape-configurable transformers.