The microscopic defects with respect to the cladding layer are often detected using a microscope, energy dispersive X-ray spectroscopy, and scanning electron microscope, etc. Even though cracks can be accurately observed using these methods, the obtained results are not convincing. The sample profile is used to observe the performance of the test sample; however, the local area of the section does not represent the entire cladding layer. The randomness is considerably large, and the detection area is small. Furthermore, the requirement of sample size is high. To solve these problems, we use laser-induced breakdown spectroscopy (LIBS) technology to detect the microscopic defects observed with respect to the cladding layer. Subsequently, different contents were obtained with respect to the TiC/Ni35 cladding samples, and different types of defects could be observed in the samples after cladding. The characteristic spectra of the sample surface can be observed in the 21 mm×4.2 mm region, and the region scanning results are obtained using the array matrix method. The results prove that LIBS technology can be used to rapidly characterize the microscopic defects in the cladding layer. According to the evaluation, the No. 4 sample has the most defects, the No. 1 and No. 5 sample defects are moderate, and the No. 2 and No. 3 sample defects are the lowest.