This paper presents a methodology for assessing the variability of biodegradable chemical oxygen demand (COD) fractions in urban wastewaters. Thirteen raw wastewater samples from combined and separate sewers feeding the same plant were characterised, and two optimisation procedures were applied in order to evaluate the variability in biodegradable fractions and related kinetic parameters. Through an overall optimisation on all the samples, a unique kinetic parameter set was obtained with a three-substrate model including an adsorption stage. This method required powerful numerical treatment, but improved the identifiability problem compared to the usual sample-to-sample optimisation. The results showed that the fractionation of samples collected in the combined sewer was much more variable (standard deviation of 70% of the mean values) than the fractionation of the separate sewer samples, and the slowly biodegradable COD fraction was the most significant fraction (45% of the total COD on average). Because these samples were collected under various rain conditions, the standard deviations obtained here on the combined sewer biodegradable fractions could be used as a first estimation of the variability of this type of sewer system.