Several hydrophobically alpha- and alpha,omega-end-capped poly(ethylene oxide) polymers were studied by light scattering below and above their critical association concentration, in order to understand their association mechanisms. In the case of monofunctionalized PEO, a one-step closed association model well fits the experimental data, with a limit number of aggregation of about 30, consistent with other experimental data and a theoretical approach. In the case of difunctionalized PEO, a good description of the experimental data is obtained by assuming a two-step association process: at low concentration, the formation of “flower-like” micelles is well described by a closed association model, whereas at higher concentration, the progressive bridging of these “flowers” can be modeled by an open association.