Diesel particulate filters (DPFs) are essential particulate matter emission control devices. Some diesel particulate filters have been observed to fail during industrial-fleet vehicle use. DPFs that fail during vehicle use compromise particulate matter emission capture. Herein, failures in cordierite DPF substrates observed during commercial fleet use were characterized as pinhole failure, melt failure, crack failure, and fouling failure. The observed failures were correlated to particulate matter chemical composition and physical changes in the cordierite substrate of the exhausted DPFs. The physical-chemical characteristics of pinhole failure, melt failure, crack failure, and fouling failure were determined by applying scanning electron microscopy-energy dispersive spectrometry (SEM-EDS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Results indicate that the chemical composition and crystalline structures of cordierite DPF substrate changed according to the failure characterization. The specific changes to the cordierite substrate during failure can contribute towards understanding fundamental DPF failure mechanisms.