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To understand the interrelationship between the microstructure and degradation behavior of poly(lactic acid) (PLA), single-walled carbon nanotubes (CNTs) were introduced into PLA as nucleating agents. The degradation behavior of PLA-CNT nanocomposites was examined under accelerated weathering conditions with exposure to UV light, heat, and moisture. The degradation mechanism proceeded via the Norrish type II mechanism of carbonyl polyester. Differential scanning calorimetry (DSC) studies showed an increase in glass transition temperature, melting temperature, and crystallinity as a result of the degradation. However, pure PLA showed higher degradation as evidenced by increased crystallinity, lower onset decomposition temperature, embrittlement, and a higher number of micro-voids which became broader and deeper during degradation. In the PLA-CNT nanocomposites, CNTs created a tortuous pathway which inhibits the penetration of water molecules deeper into the polymer matrix, making PLA thermally stable by increasing the initial temperature of mass loss. CNTs appear to retard PLA degradation by impeding mass transfer. Our study will facilitate designing environmentally friendly packaging materials that display greater resistance to degradation in the presence of moisture and UV light.