The fluorescence decay of the phenoxy group of two monodisperse and one polydisperse (Triton X-100) polyoxyethylene alkyl phenols has been studied in aqueous solution, and in the adsorbed state on a hydrophilic (hydroxylated) or hydrophobic (methylated) silica surface. In aqueous solution, below the CMC, one single exponential decay is observed with a lifetime of 4.5 nsec. Above the CMC, a second exponential component with a lifetime of 37 nsec appears with the monodisperse compounds, but not with Triton X-100. This long decay is assigned to dimeric species and its amplitude is quantitatively correlated to the fraction of molecules involved in micellar aggregates. On the hydrophilic silica surface, the same long decay appears from the very beginning of the adsorption isotherm and its amplitude remains constant up to the plateau of the isotherm, close to the value observed in the pure liquid surfactant. This is taken as evidence that, from the outset of adsorption, the majority of molecules is involved in molecular aggregates. On the hydrophobic surface, the constant amplitude regime is observed only at high surface coverage. At low surface coverage, the amplitude increases linearly with θ, suggesting that, in this regime, the adsorbed phase can be described as a dilute gas.