Litter decomposition involves multiple complex processes, including interactions between the physicochemical characteristics of litter species and various environmental factors. We selected four representative pine species in South Korea (Pinus densiflora Siebold & Zucc., Pinus thunbergii Parl., Pinus koraiensis Siebold & Zucc., and Pinus rigida Miller) to investigate the decay rate and effects of the physicochemical properties on decomposition. Needle litters were incubated in microcosms at 23 °C for 280 days and retrieved four times in about 70-day intervals. The mass loss showed significant differences among the species and was higher in the order of P. densiflora (30.5%), P. koraiensis (27.8%), P. rigida (26.5%), and P. thunbergii (23.6%). The needle litter decomposition showed a negative relationship with the initial surface area, volume, density, cellulose content, and lignin/nitrogen of the litter, and a positive relationship with the initial specific leaf area (SLA), surface-area-to-volume ratio (SA/V), and water- and ethanol-soluble substances. The decomposition rate was highly affected by the physical properties of litter when compared with the initial chemical litter quality, and it was strongly influenced by SLA and SA/V. Accordingly, the physical properties of pine needle litter, especially SLA and SA/V, may be the key factors, and they could be used as predictive indices for the decomposition rate of pine tree litters.