A method was developed to prepare asymmetric end-capped poly(ethylene oxide)s (PEOs), containing an alkyl group on one chain end and a perfluoroalkyl group on the other one (C18H37-PEO-C2H4-C8F17 and C18H37-PEO-C10H20-C8F17). These new telechelic associative polymers (APs) were synthesized by anionic polymerization of ethylene oxide initiated by an alkoxide (C18H37-O-K+) followed by esterification. The rheological behavior of asymmetric and analogous symmetric APs in aqueous solutions has been investigated as a function of polymer concentration (C), hydrophobic end-cap and surfactant used to homogenize the system: sodium dodecyl sulfate (SDS) or lithium perfluorooctyl sulfonate (LiFOS). A steep increase of the static viscosity η, attributed to the formation of a multiconnected network, is observed for C ≈ 1 wt %. Semidilute solutions present a Maxwellian rheological behavior with only one relaxation time τ associated with the least hydrophobic end group. The viscoelastic response is modified by the interactions between hydrophobic end groups and surfactant inside mixed aggregates.