To improve the colorability of keratin fibers at lower temperatures, we developed a novel coloring method using poly(ethylene imine) (PEI) as a counterion reagent (human hair was treated beforehand with a PEI solution and then was colored with an acid dye). As a result of this new method, the coloring and color fastness to shampooing clearly improved with respect to the usual method. Next, to study the coloring mechanism with PEI, we investigated the penetration of PEI and Orange II into bleached human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into bleached human hair increased with an increasing PEI treatment time and with a decreasing PEI molecular weight. With these experiments, we demonstrated that PEI, which penetrated the cortex region, exerted counterionization on Orange II, thereby increasing the penetration of Orange II into bleached human hair. (C) 2003 Wiley Periodicals, Inc.