The long-term use of a piezoelectric smart structure make it difficult to judge whether the structure or piezoelectric lead zirconate titanate (PZT) is damaged when the signal changes. If the sensor fault occurs, the cases and degrees of the fault are unknown based on the electromechanical impedance method. Therefore, after the principal component analysis (PCA) of six characteristic indexes, a two-component solution that could explain 99.2% of the variance in the original indexes was obtained to judge whether the damage comes from the PZT. Then LibSVM was used to make an effective identification of four sensor faults (pseudo soldering, debonding, wear, and breakage) and their three damage degrees. The result shows that the identification accuracy of damaged PZT reached 97.5%. The absolute scores of PCA comprehensive evaluation for structural damages are less than 0.5 while for sensor faults are greater than 0.6. By comparing the scores of the samples under unknown conditions with the set threshold, whether the sensor faults occur is effectively judged; the intact and 12 possible damage states of PZT can be all classified correctly with the model trained by LibSVM. It is feasible to use LibSVM to classify the cases and degrees of sensor faults.