Critically ill patients often lack cognitive or communicative functions, making it challenging to assess their pain levels using self-reporting mechanisms. There is an urgent need for an accurate system that can assess pain levels without relying on patient-reported information. Blood volume pulse (BVP) is a relatively unexplored physiological measure with the potential to assess pain levels. This study aims to develop an accurate pain intensity classification system based on BVP signals through comprehensive experimental analysis. Twenty-two healthy subjects participated in the study, in which we analyzed the classification performance of BVP signals for various pain intensities using time, frequency, and morphological features through fourteen different machine learning classifiers. Three experiments were conducted using leave-one-subject-out cross-validation to better examine the hidden signatures of BVP signals for pain level classification. The results of the experiments showed that BVP signals combined with machine learning can provide an objective and quantitative evaluation of pain levels in clinical settings. Specifically, no pain and high pain BVP signals were classified with 96.6% accuracy, 100% sensitivity, and 91.6% specificity using a combination of time, frequency, and morphological features with artificial neural networks (ANNs). The classification of no pain and low pain BVP signals yielded 83.3% accuracy using a combination of time and morphological features with the AdaBoost classifier. Finally, the multi-class experiment, which classified no pain, low pain, and high pain, achieved 69% overall accuracy using a combination of time and morphological features with ANN. In conclusion, the experimental results suggest that BVP signals combined with machine learning can offer an objective and reliable assessment of pain levels in clinical settings.