Despite their mass production and large applications, polyolefins' stability and durability toward the air, moisture, and weather resistance is a challenge for the ecosystem. After long-term exposure to ultraviolet (UV) radiation or high-temperature or erosion, polyolefins undergo degradation generating microplastics (MPs). The MPs generated after the degradation of these polyolefins are hazardous for the ecosystem. In the present work, we have carried out density functional theory (DFT) studies to investigate the photodegradation of six different polyolefins ranging from polyethylene to polydecene, differing in side-chain. Herein, we have investigated photooxidized derivatives of different polyolefins and analyzed their relative stability, conformations, UV-visible spectral behavior, and carbonyl index. The photooxidized derivatives of various polyolefins formed during degradation are examined. The timedependent density functional theory analysis confirms that the carbonyl groups of photooxidized products show absorption peak in Infrared (IR) and visible region, acting as light-absorbing species. The relative stabilities of hydroperoxide formed during photo/thermal oxidation of different polyolefins have been evaluated to explain the degradation behavior. The oligomerization and stabilization energies of their corresponding hydroperoxide's were computed and analyzed to explain the degradation behavior of the polyolefins. The computed results suggest that polyolefins in their pristine state are stable toward photooxidation, but chemical impurities like carbonyl, unsaturated carbonyl, carboxylic acid, and hydroperoxide derivatives make them prone to undergo degradation, a fundamental process leading to generation of MPs. The comparative results confirmed that the side-chain length affects the stability and degradation of different polyolefins toward photooxidation.