Laser cleaning is a non contact, highly controllable process for the removal of contaminants from a surface with minimum or no damage to the substrate material. Laser cleaning has been applied mainly on flat and curved surfaces. Little is known on the phenomena and feasibility of laser cleaning of slotted structures. Slots are common structures in engineering, and can be found in many components. In this PhD work, the feasibility of laser cleaning of alpha case on flat titanium alloy surfaces was initially explored, and then an investigation was made on the use of a pulsed laser for the cleaning of micro to macro slots in silicon and metallic materials. The effects of laser processing parameters on the contaminant removal from these slots were experimentally studied. Laser cleaning thresholds and cleanliness was examined. Meanwhile, finite element modelling (FEM) and time domain finite difference modelling techniques were used to simulate the processes involved to aid the understanding of the technique for process optimisation. The experiments were undertaken to verify if such models are able to accurately predict the cleaning thresholds. The surface and sub-surface characteristics before and after laser cleaning were examined using optical microscopy and scanning electron microscopy (SEM). It has been shown that the slot structure and its material properties were not damaged or changed by laser cleaning process. A novel contribution is that surface morphology after the laser ablation could be used as a diagnostic method to indentify the presence of alpha case and measure its thickness due to the specific characteristics of the surface roughness and generated cracks on the ablated surface after laser irradiation. Besides, it has been found that an axial beam which propagates into the narrow slots can successfully clean the tiny particles on the slot sidewalls whose width ranges from 3.5 mm to 13mm. These phenomena had never been reported before.