The ionization of laser-ablated vapours with lasers producing ns duration pulses at various wavelengths has been studied in order to understand the mechanisms of the vapour–plasma transition. It has been established that there are several regimes characterizing the laser–target interaction which depend on laser intensity, wavelength, and pulse duration. The range of laser intensities for optimal laser evaporation is determined by the condition of transparent vapours. The intensity range is upper-limited by the opaque plasma formation due to vapour optical breakdown. Results are given for laser evaporation of graphite with Nd:YAG laser (1.064 μm), KrF laser (248 nm) and ArF laser (193 nm). For the UV laser wavelength the regime of skin-effect interaction was proposed as the mechanism of ion acceleration, and the range of validity of the skin-effect mode was established. With UV lasers the interaction has a bimodal nature: the interaction may proceed initially in the skin effect regime, resulting in a few high-energy ions, until hydrodynamic expansion begins at a later stage. The skin-effect interaction at the initial stage of the UV laser pulse gives the first, to our knowledge, explanation for the acceleration of ions up to ∼100 eV at low laser intensities of 108–109 W/cm2 and ns-range pulse duration.