We used polyethyleneglycol (PEG) as a modulator to manipulate pore and cell sizes in the porous anodic alumina (PAA) fabrication. It is shown for the first time that continuous manipulation of the pore size of PAA can be realized. Combined with the coexistent cell-size controlling effect, the morphology and properties of this important nanoscale template and separation membrane can be precisely regulated. The pore size modulation mechanism is proposed on the basis of the morphological and electrochemical results. The presence of PEG in the electrolyte results in a more compacted structure of the barrier layer alumina (BLA), although the barrier layer thickness does not change considerably. In addition, the additive can obviously restrain the chemical dissolution of alumina and shape smaller pores. These two effects combined with the increased viscosity of the electrolyte slow down the ion transportation and diminish the anodization current. Thus, the burning-down phenomena of the aluminum substrates can be avoided at relatively high voltage anodization, and an interpore distance up to 610 nm can be achieved.