Physiological responses to pain have received increasing attention among researchers for developing an automated pain recognition sensing system. Though less explored, Blood Volume Pulse (BVP) is one of the candidate physiological measures that could help objective pain assessment. In this study, we applied machine learning techniques on BVP signals to device a non-invasive modality for pain sensing. Thirty-two healthy subjects participated in this study. First, we investigated a novel set of time-domain, frequency-domain and nonlinear dynamics features that could potentially be sensitive to pain. These include 24 features from BVP signals and 20 additional features from Inter-beat Intervals (IBIs) derived from the same BVP signals. Utilizing these features, we built machine learning models for detecting the presence of pain and its intensity. We explored different machine learning models, including Logistic Regression, Random Forest, Support Vector Machines, Adaptive Boosting (AdaBoost) and Extreme Gradient Boosting (XGBoost). Among them, we found that the XGBoost offered the best model performance for both pain classification and pain intensity estimation tasks. The ROC-AUC of the XGBoost model to detect low pain, medium pain and high pain with no pain as the baseline were 80.06 %, 85.81 %, and 90.05 % respectively. Moreover, the XGboost classifier distinguished medium pain from high pain with ROC-AUC of 91%. For the multi-class classification among three pain levels, the XGBoost offered the best performance with an average F1-score of 80.03%. Our results suggest that BVP signal together with machine learning algorithms is a promising physiological measurement for automated pain assessment. This work will have a national impact on accurate pain assessment, effective pain management, reducing drug-seeking behavior among patients, and addressing national opioid crisis.