Intrachain exciton quenching in ladder-type polyparaphenylene has been quantified for the first time. Two-phonon absorption and subsequent upconverted photoluminescence of ladder-type polyparaphenylene and polyfluorene has been measured and analyzed with a new theoretical framework for the two-photon absorption saturation. This microscopic analysis determines the number of singlet excitons as a function of the excitation intensity, which is compared to the photoluminescence intensity. The absorption saturation alone perfectly describes the photoluminescence saturation in polyfluorene, whereas in ladder-type polyparaphenylene, exciton-exciton quenching occurs. By measuring in solution, the formation of stacked polymer chains is prevented. Therefore, the quenching is due to intrachain interaction.