This report demonstrates that novel XAFS (X-ray absorption fine structure) microimaging, which does not require any spatial scans of the sample, can be used to evaluate the chemical states of combinatorial array libraries. The method has been applied to manganese-cobalt spinel MnCo2O4 prepared on the same substrate under different synthesis conditions. The valence numbers of Mn have been studied as a map by obtaining X-ray fluorescence images (1000 x 1000 pixels) as a function of the incident energy of synchrotron X-rays. The advantage of this method is that the whole substrate, i.e., all samples in the library, can be observed in a short time, typically ca. 10 min, which is equivalent to the measuring time for a single sample on the substrate when conventional scanning methods are employed.