In this work, we report the influence of surfactant chain length and surfactant concentration on the photoluminescence (PL) of water-soluble pi-conjugated poly(thienyl ethylene oxide butyl sulfonate) (PTE-BS). We have used alkylammomium surfactants with 8, 9, 10, and 12 carbon atoms per hydrocarbon chain. The surfactant concentration was varied from 0.125 the critical micelle concentration (CMC) up to 2 times the CMC. The results show that at premicellar concentrations all the surfactants promote the polymer aggregation inducing an increase in the interchain charge transfer by pi-pi interactions, which competes with PL emission processes. However, in the premicellar range, the polymer PL emission is sharply affected by the surfactant chain length. Thus, the PL is quenched by the surfactants with the shortest tails, whereas the surfactants with the longest ones provoke an enhancement of the PL emission. This behavior has been associated with the capacity of the surfactants with the longest hydrocarbon chains to accommodate their tails inside the polymer, obstructing the appearance of pi-pi interchain interactions during aggregation and reducing intrachain defects. By contrast, at the CMC, the surfactant chain length does not modify the PL emission, since the excess of surfactant inhibits polymer aggregation, thus enhancing the efficiency of light emissive processes.