Objective: To investigate the feasibility of the detection of brief orofacial pain sensations from easily recordable physiological signals by means of machine learning techniques. Approach: A total of 47 subjects underwent periodontal probing and indicated each instance of pain perception by means of a push button. Simultaneously, physiological signals were recorded and, subsequently, autonomic indices were computed. By using the autonomic indices as input features of a classifier, a pain indicator based on fusion of the various autonomic mechanisms was achieved. Seven patients were randomly chosen for the test set. The rest of the data were utilized for the validation of several classifiers and feature combinations by applying leave-one-out-cross-validation. Main results: During the validation process the random forest classifier, using frequency spectral bins of the ECG, wavelet level energies of the ECG and PPG, PPG amplitude, and SPI as features, turned out to be the best pain detection algorithm. The final test of this algorithm on the independent test dataset yielded a sensitivity and specificity of 71% and 70%, respectively. Significance: Based on these results, fusion of autonomic indices by applying machine learning techniques is a promising option for the detection of very brief instances of pain perception, that are not covered by the established indicators.