Nanocrystalline diamond films have been synthesized on various substrates by 800 nm fs laser irradiation of a variety of organic solvents including acetone, pentane, hexane, heptane, octane, dodecane, and hexadecane in the presence of a transition metal catalyst. 632 nm Raman spectra display a strong vibration mode at 1308 cm−1 characteristic of hexagonal diamond. X-ray photoelectron spectra confirm that the film is mainly sp
3-bonded carbon containing a low concentration of sp
2-bonded inclusions. Film microstructure shows that these films are assembled from nanoparticles having an average size of < 100 nm. Analysis of the liquid after irradiation using HPLC techniques indicates that polyyne molecules are also synthesized during irradiation. It is possible that these species are formed as the products of ion chemistry following Coulomb explosion. This process may enable a new method for the creation of nanocrystalline hexagonal diamond layers for micro-electronic and other applications.