A novel method for identification of four isomers of dihydroxynaphthalene (DHN) was reported by their different perturbation effects on a Briggs-Rauscher (BR) oscillating system. In the system, macrocyclic nickel (II) complex NiL(ClO4)(2) is used as the catalyst, where the ligand L in the complex is 5,7,7,12,14,14-hexemethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. By putting equal amount of the same concentrations of four isomers (1,4-dihydroxynaphthalene (1,4-DHN), 1,5-dihydroxynaphthalene (1,5-DHN), 2,3-dihydroxynaphthalene (2,3-DHN) and 2,7-dihydroxynaphthalene (2,7-DHN)) into BR system, the system could or couldn't be perturbed, being reflected in quite different oscillating behaviors after addition of isomers. These four isomers were identified in their concentration range of 5.0 x 10(-6) to 2.5 x 10(-4) mol/L. An explanation of such perturbation mechanism is that, 1,4-DHN couldn't be oxidized by BR matrix, but 1,5-DHN, 2,3-DHN and 2,7-DHN could be oxidized by HOO center dot to yield 5-Hydrox-1,4-naphthoquinone, phthalic acid and 6,7-dihydroxyperylene-1,12-quinone (DHPQ), respectively.