AbstractDue to the critical impacts of microplastic (MP) aggregation on their fate, mobility, and bioavailability, this study developed a simple approach to examine their aggregation under varying water chemistry and MPs’ surface aging conditions. An accelerated photodegradation experiment was conducted for 6 weeks. The water chemistry conditions varied by altering pH, using natural organic matter (NOM), and conducting experiments in ultrapure water and synthetic stormwater. The surface chemistry analysis of photodegraded MPs revealed the formation of carbonyl and vinyl functional groups. Zeta potential measurements revealed a more negative surface charge for photodegraded MPs compared to new MPs. The aggregation kinetics of MPs were studied by comparing the number of MP clusters formed over time after intense dispersion in water. The results showed that the presence of NOMs reduces the aggregation tendency of new low‐density polyethylene MPs due to enhanced steric hindrance and electrostatic repulsion. However, variations of pH and utilizing synthetic stormwater versus ultrapure water did not alter the aggregation kinetics of new MPs. The aggregation behavior of photodegraded MPs was significantly different from new MPs. A greater tendency for aggregation of photodegraded MPs was found in the stormwater compared to the ultrapure water. This study contributes to a better understanding of the transport and fate of MPs within the aqueous environment and their subsequent environmental risks.