For studying chlorophyll biosynthetic heterogeneity of plants, it is necessary to establish a technique for microassay of a putative monovinyl and divinyl protoporphyrin IX. Precise determination of the amounts of monovinyl and divinyl protoporphyrin IX is difficult with optical electronic spectroscopy even at 77$circ$C. Such a problem could be solved by conversion of protoporphyrin IX to protoporphyrin IX dimethylester with diazomethane and subsequent Mg insertion into protoporphyrin IX dimethylester by reaction with a Grignard solution. The proportion of monovinyl and divinyl Mg-protoporphyrin IX dimethylester formed was measured instead of direct measuring that of protoporphyrin IX by low-temperature spectrofluorometry. The relative proportions of monovinyl and divinyl of protoporphyrin IX, Mg-protoporphyrin IX, and Mgprotoporphyrin IX dimethylester have not changed during the chemical conversion steps. This analysis system could be useful for the study of the monovinyl and divinyl chlorophyll biosynthetic routes in plants.