Non-stationary thermal wave imaging (NSTWI) techniques are primarily used to assess material properties and structural integrity without damaging a structure. Frequency-modulated thermal wave imaging (FMTWI) is a well-known NSTWI approach that uses a low-peak power heat source to examine structures in a reasonable experimentation time. Recently, various methods, such as pulse compression, Fourier transform, principal component analysis (PCA) and independent component analysis (ICA), have been introduced to handle the non-linearity of transient thermal signatures. However, handling non-linearity and developing a fully automatic defect detection system remains very challenging due to certain limitations of the aforementioned methods. To overcome these problems, this paper proposes an artificial neural network (ANN) for the identification of subsurface flaws in a mild steel sample investigated using the FMTWI approach. The accuracy and the performance of the proposed neural network (NN) are evaluated through a confusion matrix and region of convergence (ROC) analysis for the classification of defective and healthy pixels in an infrared image sequence. The developed NN model has achieved 99.7% accuracy in classifying the pixels correctly.