We have accelerated the ageing of CuAlS2 by the application of a static electrical field for different degradation times. We have investigated the admittance spectroscopy and the scanning electron microscopy to follow and understand the (mass-charge) coupled transport processes produced in the volume and on the surface of these films. The electrical constraint induces, after an incubation phase, an activated decrease of the resistance, followed by a susbstantial increase correlated to the formation of an open circuit. This degradation occurs more rapidly for the films having initially a lower resistance, due to the thermal dissipation which increases considerably the temperature to about 140 °C. Admittance spectra reveal, at low frequencies, a capacitive loop related to the formation of a charge space induced by copper diffusion. Such migration develop induces the formation of copper arborescences, spreading from the cathode towards the anode. The effect of these structures on the properties of the degraded films is discussed in relation to electromigration and associated processes (whiskers, fracture, healing, bridge-building, ...). Also, we have noticed their similarity with fractal phenomena such as electrodeposition and dielectric breakdown.