Taking advantage of both the self-organizing characteristics and the amphiphilic property of poly(styrene-block-ethyleneoxide) (P(S-b-EO)), we have realized one-step fabrication of nanoelectrode ensembles (NEEs). By choosing the electrolyte solution elaborately, only the poly(ethylene oxide) (PEO) segment in the P(S-b-EO) film was swollen to serve as nanoscale tunnels for solvated ions, whereas the polystyrene segment remained robust to be the electrode mask. An electrochemical analysis indicated that a transition between linear diffusion and nonlinear diffusion could be observed due to the small diffusion coefficient of ferrocene in PEO nanodomains.