[Figure: see text]. Laser ablation harnesses photon energy to remove material from a surface. Although applications such as laser-assisted in situ keratomileusis (LASIK) surgery, lithography, and nanoscale device fabrication take advantage of this process, a better understanding the underlying mechanism of ablation in polymeric materials remains much sought after. Molecular simulation is a particularly attractive technique to study the basic aspects of ablation because it allows control over specific process parameters and enables observation of microscopic mechanistic details. This Account describes a hybrid molecular dynamics-Monte Carlo technique to simulate laser ablation in poly(methyl methacrylate) (PMMA). It also discusses the impact of thermal and chemical excitation on the ensuing ejection processes. We used molecular dynamics simulation to study the molecular interactions in a coarse-grained PMMA substrate following photon absorption. To ascertain the role of chemistry in initiating ablation, we embedded a Monte Carlo protocol within the simulation framework. These calculations permit chemical reactions to occur probabilistically during the molecular dynamics calculation using predetermined reaction pathways and Arrhenius rates. With this hybrid scheme, we can examine thermal and chemical pathways of decomposition separately. In the simulations, we observed distinct mechanisms of ablation for each type of photoexcitation pathway. Ablation via thermal processes is governed by a critical number of bond breaks following the deposition of energy. For the case in which an absorbed photon directly causes a bond scission, ablation occurs following the rapid chemical decomposition of material. A detailed analysis of the processes shows that a critical energy for ablation can describe this complex series of events. The simulations show a decrease in the critical energy with a greater amount of photochemistry. Additionally, the simulations demonstrate the effects of the energy deposition rate on the ejection mechanism. When the energy is deposited rapidly, not allowing for mechanical relaxation of the sample, the formation of a pressure wave and subsequent tensile wave dominates the ejection process. This study provides insight into the influence of thermal, chemical, and mechanical processes in PMMA and facilitates greater understanding of the complex nature of polymer ablation. These simulations complement experiments that have used chemical design to harness the photochemical properties of materials to enhance laser ablation. We successfully fit the results of the simulations to established analytical models of both photothermal and photochemical ablation and demonstrate their relevance. Although the simulations are for PMMA, the mechanistic concepts are applicable to a large range of systems and provide a conceptual foundation for interpretation of experimental data.