Metallic titanium (Ti(0)) nanoparticles, 1.5 ± 0.4 nm in diameter, are obtained via lithium naphthalenide ([LiNaph])-driven reduction of TiCl4× 2THF in tetrahydrofuran (THF). HRTEM, fast Fourier transformation (FFT), optical spectra and X-ray absorption near edge structure (XANES) confirm their chemical composition. Besides their pyrophoric properties, their high reactivity is validated by direct transformation of Ti(0) into TiC maintaining the size.