The local crystallization during annealing at 600 °C in nanoscale diamond-like carbon coatings films grown by pulsed vacuum-arc deposition method was observed using modern techniques of high-resolution transmission electron microscopy. The crystallites formed by annealing have a face-centred cubic crystal structure and grow in the direction [01¯1¯] as a normal to the film surface. The number and size of the crystallites depend on the initial values of the intrinsic stresses before annealing, which in turn depend on the conditions of film growth. The sizes of crystallites are 10 nm for films with initial compressive stresses of 3 GPa and 17 nm for films with initial compressive stresses of 12 GPa. Areas of local crystallization arising during annealing have a structure different from the graphite. Additionally, the investigation results of the structure of nanoscale diamond-like carbon coatings films using Raman spectroscopy method are presented, which are consistent with the transmission electron microscopy research results.