Interest in pulsed laser deposition (PLD), as a technology producing thin layers of complex materials is growing exponentially in recent years. Condensation from the vapour phase at rapid solidification favours the nano-structure formation in the thin layers. Deposition of virtually any materials, from pure elements to multicomponent compounds, on various substrate, makes PLD very suitable technology in fabrication of thin layers of nano-structure type for wide range of application. Examinations on the PLD layers of FeAl and Ni3Al intermetallics produced using an excimer KrF are presented. The thickness of deposited layers was dependent on substrate temperature and ion energy. Nano-structure to fine-grained micro-structure in the range from 50 to 1000 nm was formed in deposited thin layer in respect to the deposition conditions. The stoichiometry transfer was under examination in the case of the ablated FeAl and Ni3Al targets. Titanium nitride thin layers were fabricated by PLD using a Nd:YAG laser on both metallic (ferritic steel and metallic titanium) and non-metallic (polyurethane) substrates by ablation of pure titanium in nitrogen environment. Deposition of the BN from the h-BN target was performed with application of an excimer ArF laser. Complex structure examinations of microstructure, texture and residual stresses were performed using XRD, SEM, TEM and AFM.