The formation of crystalline diamond films from amorphous diamond‐like carbon films by pulsed laser irradiation with a 300 μs non‐Q‐switched Nd:YAG laser has been established by a combined study of transmission electron microscopy, x‐ray photoelectron spectroscopy, and electrical resistivity. The films have been prepared by glow discharge decomposition of a mixture of propane, n‐butane, and hydrogen in a rf plasma operating at a frequency of 13.56 MHz. Prior to laser irradiation, the films have been found to be amorphous by transmission electron microscope studies. After irradiation, the electron diffraction patterns clearly point out the formation of cubic diamond structure with a lattice spacing of 3.555 Å. However, the close similarity between diamond and graphite electron diffraction patterns could sometimes be misleading regarding the formation of a diamond structure, and hence, x‐ray photoelectron spectroscopic studies have been carried out to confirm the results. A chemical shift in the C 1s core level binding energies towards higher values, viz., from 286.5 to 287.8 eV after laser irradiation, and a high electrical resistivity >1013 Ω cm are consistent with the growth of diamond structure. This novel ‘‘low‐temperature, low‐pressure’’ synthesis of diamond films offers enormous potential in terms of device compatibility with other solid‐state devices.