An investigation aiming to seek a correlation between ablation rates and various polymer thermal properties, based on experimental ablation data generated for 14 polymers commonly used in microfluidics, is presented. A statistical analysis was carried out for laser fluence against various polymer descriptors and/or their combinations. The results of the analysis show a relatively high correlation coefficient of 0.82 for polymer ablation data when we compare fluence against the product of ablation rate and the difference between the glass transition temperature and room temperature. The effects of polymer properties are also illustrated by an investigation of ablation behaviour of DNQ/novolak thin films, which had been exposed to different levels of UV radiation prior to laser ablation, using atomic force microscopy. The surface characteristics of the thin films following laser irradiation are discussed in terms of differences in laser absorption and the glass transition temperature of the films. The results are consistent with the glass transition temperature being a critical factor affecting laser/polymer interaction.