The synthesis of nanodiamonds by pulsed-laser ablation in liquid (PLAL) is an attractive research field in developing well-dispersed fluorescent nanodiamonds for bioimaging and life science. However, nanodiamonds are quite different from their widely pursued carbon allotropes both in synthesis conditions and physical properties. It is a great challenge to synthesize metastable phase nanodiamonds that prefer high temperature and high pressure. Despite the progress in the synthesis of nanodiamond by pulsed-laser ablation of graphite target using different laser power densities under room conditions, the transformation from graphite to nanodiamonds are not yet well explained. In order to have a better understanding to the formation of metastable nanodiamonds upon PLAL, the formation of nanodiamond has been elucidated from both the aspects of thermodynamics and kinetics. Due to low laser intensity and long wavelength, synthesis of nanodiamonds is the result of high cooling velocity of high-pressure and high-temperature carbon vapor condensation formed under laser vaporization of graphite particles. When diamond nuclei grow into the right size, they cannot increase and the graphite nucleation begins to form and grow on the diamond at given conditions due to long pulse width for ms-pulsed laser. In fact, the diamond particles enwrapped several layers of graphite have obtained. Moreover, the reasons related 3~6nm diamonds prepared by this new process and having narrow size distribution are also discussed.