This work deals with the determination of polymer effective charge based on the sensitivity of detection in capillary electrophoresis using indirect UV detection. In this detection mode, the polyelectrolyte (solute) displaces a certain quantity of probe contained in the background electrolyte and having the same charge as the solute. This quantity of displaced probe is directly correlated to the effective charge of the solute. Contrary to other electrophoretic methods generally used for monitoring chances in effective charge, this methodology is not based on the effective mobility of the polyelectrolyte (i.e., migration times) but on the sensitivity of detection (i.e., peak areas). Experimental values of effective charge obtained for statistical copolymers of poly(acrylamide-co-sodium 2-acrylamido-2-methylpropanesulfonate), for homopolymers of poly(diallyldimethylammonium chloride), poly(acrylic acid), and poly(metacrylic acid), are compared to the Manning theory of charge condensation. Interestingly, this methodology can be used for the characterization of macromolecular architecture since the effective charge of copolymers highly depends on the repartition of the charged monomers along the polymer chain. As an example, this methodology can easily distinguish statistical copolymers from diblock copolymers of similar chemical charge densities. Experiments were carried out on diblock copolymers of poly(acrylic acid)-b-poly(ethylene oxide) (PAA-b-PEO) and poly(methacrylic acid)-b-poly(ethylene oxide) (PMAA-b-PEO). The variation of the sensitivity of detection of statistically charged copolymers in the indirect UV mode with the chemical charge density is also discussed in detail.