Pulsed laser ablation has been investigated as a method for the creation of thick segmented scintillator arrays for high-energy X-ray radiography. Thick scintillators are needed to improve the X-ray absorption at high energies, while segmentation is required for spatial resolution. Monte-Carlo simulations predicted that reflections at the inter-segment walls were the greatest source of loss of scintillation photons. As a result of this, fine pitched arrays would be inefficient as the number of reflections would be significantly higher than in large pitch arrays. Nanosecond and femtosecond pulsed laser ablation was investigated as a method to segment cadmium tungstate (CdWO_4). The effect of laser parameters on the ablation mechanisms, laser induced material changes and debris produced were investigated using optical and electron microscopy, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy for both types of lasers. It was determined that nanosecond ablation was unsuitable due to the large amount of cracking and a heat affected zone created during the ablation process. Femtosecond pulsed laser ablation was found to induce less damage. The optimised laser parameters for a 1028 nm laser was found to be a pulse energy of 54 μJ corresponding to a fluence of 5.3 J cm^-2 a pulse duration of 190 fs, a repetition rate of 78.3 kHz and a laser scan speed of 707 mm s^-1 achieving a normalised pulse overlap of 0.8. A serpentine scan pattern was found to minimise damage caused by anisotropic thermal expansion. Femtosecond pulsed ablation was also found to create a layer of tungsten and cadmium sub-oxides on the surface of the crystals. The CdWO_4 could be cleaned by immersing the CdWO_4 in ammonium hydroxide at 45°C for 15 minutes. However, XPS indicated that the ammonium hydroxide formed a thin layer of CdCO_3 and Cd(OH)_2 on the surface. Prototype arrays were shown to be able to resolve features as small as 0.5 mm using keV energy X-rays. The most efficient prototype showed low detective quantum efficiency of 0.08±0.01 at 0 lp/mm using a tube voltage of 160 kVp.