We report a facile colloidal synthesis of gallium (Ga) nanoparticles with the mean size tunable in the range of 12-46 nm and with excellent size distribution as small as 7-8%. When stored under ambient conditions, Ga nanoparticles remain stable for months due to the formation of native and passivating Ga-oxide layer (2-3 nm). The mechanism of Ga nanoparticles formation is elucidated using nuclear magnetic resonance spectroscopy and with molecular dynamics simulations. Size-dependent crystallization and melting of Ga nanoparticles in the temperature range of 98-298 K are studied with X-ray powder diffraction, specific heat measurements, transmission electron microscopy, and X-ray absorption spectroscopy. The results point to delta (δ)-Ga polymorph as a single low-temperature phase, while phase transition is characterized by the large hysteresis and by the large undercooling of crystallization and melting points down to 140-145 and 240-250 K, respectively. We have observed size-tunable plasmon resonance in the ultraviolet and visible spectral regions. We also report stable operation of Ga nanoparticles as anode material for Li-ion batteries with storage capacities of 600 mAh g(-1), 50% higher than those achieved for bulk Ga under identical testing conditions.