Chiral separation of aryalcohols such as 1-phenyl-propanol, 1-phenyl-2-proanol, and 2-phenyl-1-propanol by capillary electrophoresis has been optimized using the overlapping resolution mapping (ORM) scheme. Three critical parameters of the electrophoretic media, i.e. phosphate concentration, sulfated ${eta}$-cyclodextrin (CD) concentration and pH, were chosen for optimization. The working ranges were initially presumed by 7 preexperiments. Further optimization was carried out by another seven experiments within the narrow working ranges. From the final overlapping resolution mapping all peak pairs, the area of maximum separations were located. Using the conditions of a point in this area, we found that the target compounds were a baseline separated within 30 min. The maximum separation conditions of arylalcohols were a chiral selector concentration of 5.4%, a phosphate concentration of 28 mM, and a pH of 5.0.