Excimer laser ablation is a versatile technique that can be used for a variety of different materials. Excimer laser ablation overcomes limitations of conventional two-dimensional (2D) microfabrication techniques and facilitates three-dimensional (3D) micromanufacturing. Previously, we have reported a characterization study on 248 nm KrF excimer laser micromachining. This paper extends the study to 193 nm ArF excimer laser micromachining on five representative micro-electro-mechanical systems (MEMS) materials (Si, soda-lime glass, SU-8, polydimethylsiloxane (PDMS), and polyimide). Relations between laser parameters (fluence, frequency and number of laser pulses) and etch performances (etch rates, aspect ratio, and surface quality) were investigated. Etch rate per shot was proportional to laser fluence but inversely proportional to number of laser pulses. Laser frequency did not show a notable impact on etch rates. Aspect ratio was also proportional to laser fluence and number of laser pulses but was not affected by laser frequency. Materials absorbance spectrum was found to have important influence on etch rates. Thermal modeling was conducted as well using numerical simulation to investigate how the photothermal ablation mechanism affects the etching results. Thermal properties of material, primarily thermal conductivity, were proved to have significant influence on etching results. Physical deformation in laser machined sites was also investigated using scanning electron microscopy (SEM) imaging. Element composition of redeposited materials around ablation site was analyzed using energy dispersive x-ray spectroscopy (EDXS) analysis. Combined with our previous report on KrF excimer laser micromachining, this comprehensive characterization study provides guidelines to identify optimized laser ablation parameters for desired microscale structures on MEMS materials. In order to demonstrate the 3D microfabrication capability of ArF excimer laser, cutting and local removal of insulation for a novel floating braided neural probe made of polyimide and nichrome was conducted successfully using the optimized laser ablation parameters obtained in the current study.