This work presents results from a detailed characterization of landfill leachates of different ages from a landfill in a major Brazilian city. This characterization consists of determining the molecular size distribution and the inert chemical oxygen demand (COD) and the biodegradability of both aerobic and anaerobic processes. Results show that leachate with a high COD concentration leachate has low biodegradability. A significant fraction of the COD is not characterized as protein, carbohydrate, or lipids, which reinforces the hypothesis that the remaining fraction was present in all leachate fractions (less than 1 kDa; between 1 and 10 kDa; between 10 and 100 kDa; and greater than 100 kDa) and is refractory. These results suggest that leachates with such characteristics require treatment systems that use physical-chemical processes as a pre- or post-treatment step to biological processes.