Vitamin E is an essential nutrient, but its poor water solubility limits food and pharmaceutical applications. The usability of vitamin E can be enhanced via modification methods such as encapsulation, which transforms the physical state of vitamin E from a liquid to a powder. This study examined the efficacy of near-infrared (NIR) and mid-infrared (MIR) spectroscopy in identifying and predicting various vitamin E derivatives in vitamin E-encapsulated powder (VEP). An MIR analysis revealed the fundamental C–H vibrations of vitamin E in the range of 2700–3250 cm⁻¹, whereas an NIR analysis provided information about the corresponding combination, first, and second overtones in the range of 4000–9000 cm⁻¹. The MIR and NIR data were analyzed using a principal component analysis to characterize the VEP. Partial least squares (PLS) regression was applied to predict the content of individual vitamin E derivatives. PLS cross-validation revealed that NIR analysis provides more reliable predictive accuracy and precision for the contents of vitamin E derivatives, achieving a higher coefficient of determination for prediction (Q²) (0.92–0.99) than MIR analysis (0.20–0.85). For test set validation, the NIR predictions exhibited a significant level of accuracy, as indicated by a high ratio of prediction to deviation (RPD) and Q². Furthermore, the PLS models developed using the NIR data had statistically significant predictive performance, with a high RPD (1.54–3.92) and Q² (0.66–0.94). Thus, NIR spectroscopy is a valuable nondestructive technique for analyzing vitamin E samples, while MIR spectroscopy serves as a useful method for confirming its presence.