We studied the structural transformation of diamond-like amorphous carbon (a-C) films into ultrahard carbon nanocomposites via postannealing to 600 °C using transmission electron microscopy, x-ray reflectivity, and small-angle scattering. Film density decreases monotonically above 200 °C. Film surfaces roughen upon annealing to 300 °C; however, a-C recovers its smoothness with higher temperature annealing. Finally, there exists some quasiperiodic nanostructural feature with a lattice spacing that increases with annealing, correlating well with purely a-C nanocomposite structures imaged from samples annealed at 600 °C. We propose that these annealing-induced nanostructural changes are a derivative of localized stress fields in as-grown a-C films. © 2001 American Institute of Physics.