Electrical tapes are recovered during criminal investigations as physical evidence in cases of rape, kidnapping, and explosion incidents. The analysis of such evidence can provide an evidentiary link between the suspect, the victim, object, or the crime scene. In the present study, 25 brands of electrical tapes have been analyzed using ATR‐FTIR (attenuated total reflectance Fourier transform infrared) spectroscopy. Samples (1 cm2) were analyzed in the mid IR (Infrared) region from 4000–600 cm−1, and the functional groups of various components have been profiled. Chemometric methods‐PCA (principal component analysis) and PCA‐LDA (linear discriminant analysis) have been employed to interpret the data and classify the samples into its respective classes. Preliminary assessment of sample clustering due to similar chemical composition was visualized using PCA. PCA‐LDA applied for classification purpose yielded classification accuracy (calibration) of 92.98% for the adhesive side and 88% for the backing side. The validation results showed classification accuracy of 89.47% for the adhesive side and 84% for the backing side. Blind validation study was carried out using 5 samples, and classification accuracy of 100% and 80% was obtained for the adhesive and the backing side, respectively. In the current study, a preliminary substrate study was carried out, and the results showed that the backing samples could be more accurately matched to their correct source of origin than the adhesive side.