Multiwavelength Raman microspectroscopy (MWRM) analysis for characterization of soot structure and reactivity was developed. This new method is based on the dispersive character of carbon D mode in Raman spectra (i.e., red shift and increase in intensity at higher excitation wavelength, λ(0)). The approach was proven by investigating various diesel soot samples and related carbonaceous materials at different λ(0) (785, 633, 532, and 514 nm). In order to compare the behavior of the D mode for various samples and to derive a single parameter characterizing the soot structure, the difference of integrals for pairs of spectra collected at different λ(0) was calculated. MWRM analysis revealed substantial differences in the structural ordering which decreases from graphite, over Printex XE2 and various diesel soot samples, to spark discharge soot. To obtain the relation between structure and reactivity of soot, MWRM analysis was combined with temperature-programmed oxidation (TPO). TPO allowed us to characterize the oxidation behavior of soot in terms of the maximum emission (CO + CO(2)) temperature and reactivity index. The latter was calculated by introducing the reactivity limits: spark discharge soot containing a large amount of disorder represents the upper limit, whereas the lower limit is given by graphite powder with high structural order. The comparison of MWRM (viz., the observed Raman difference integrals) and TPO data revealed a linear correlation between soot structure and oxidation reactivity. Thus, we demonstrated for the first time the potential of MWRM for a robust and rapid prediction of diesel soot reactivity based on the structure-reactivity correlation.