The study investigated the particle size distribution of major organic pollutants in black water and gray water fractions of domestic sewage. Particle size distribution was assessed by means of a filtration/ultrafiltration sequence together with laser diffraction. Emphasis was placed upon the correlation between the size distribution of chemical oxygen demand (COD) and its biodegradation characteristics obtained by respirometric analysis. Particle size distribution analysis provided specific fingerprints for COD, total organic carbon (TOC), carbohydrates, proteins, and color for black water and gray water: Aside from significant difference between COD contents, the more concentrated COD was predominantly in particulate form in black water, whereas soluble COD accounted for nearly 60% of the total in gray water. TOC and carbohydrate exhibited a similar pattern. Size distribution of particulate matter yielded different characteristics for the two fractions and indicated that settleable matter should be considered as a significant portion in assessing biodegradation. Particle size distribution of COD, although not directly related, gave an accurate image of biodegradation, indicating that particle size was basically the main parameter for differentiating and predicting major COD fractions with different biodegradation characteristics. It explained the dual hydrolysis mechanism associated with the black water based on the existence of a significant settleable COD fraction.