This paper analytically investigates the picosecond laser ablation of polymer. Laser-pulsed ablation is a well-established tool for polymer. However the ablation mechanism of laser processing for polymer has not been thoroughly understood yet. This study utilized a thermal transport model to analyze the relationship between the ablation rate and laser fluences. This model considered the energy balance at the decomposition interface as the ablation mechanisms and is applied to predict the laser-ablated depth of Acrylonitrile Butadiene Styrene/PolyVinyl Chloride (ABS/PVC). The calculated variation of the ablation rate with the logarithm of the laser fluence agrees with the measured data. The effects of material properties and processing parameters on the ablation depth per pulse are discussed for picosecond laser processing of ABS/PVC.