This chapter is mainly focused on the application of vibrational spectroscopy, namely mid‐infrared, near infrared and Raman spectroscopy, to irradiated food. The chapter begins with an introduction to the basis of radiation and the effects of radiation on biological systems; this is followed by a brief discussion on the usage of radiation in food science and the general spectroscopic methods used in the detection of irradiation. The applications of different chemometric techniques, such as principal component analysis (PCA), partial least squares regression (PLS), canonical variate analysis (CVA), linear discriminant analysis (LDA) and cluster analysis to vibrational spectroscopic data of irradiated food are presented. In addition, the discrimination of radiation dose in food using vibrational spectroscopy together with chemometric methods is described. The application of detailed molecular investigation, such as determination of content, structure, and function of macromolecules, is specifically illustrated in the analysis of hazelnut samples using mid‐IR spectroscopy. Determination of radiation‐induced lipid peroxidation and protein secondary structural alterations in food are discussed. Applications of NIR spectroscopy on irradiated food, such as determination of food quality and the effect of radiation on different food samples are also discussed.