Understanding the association between subjective emotional experiences and physiological signals is of practical and theoretical significance. Previous psychophysiological studies have shown a linear relationship between dynamic emotional valence experiences and facial electromyography (EMG) activities. However, whether and how subjective emotional valence dynamics relate to facial EMG changes nonlinearly remains unknown. To investigate this issue, we re-analyzed the data of two previous studies that measured dynamic valence ratings and facial EMG of the corrugator supercilii and zygomatic major muscles from 50 participants who viewed emotional film clips. We employed multilinear regression analyses and two nonlinear machine learning (ML) models: random forest and long short-term memory. In cross-validation, these ML models outperformed linear regression in terms of the mean squared error and correlation coefficient. Interpretation of the random forest model using the SHapley Additive exPlanation tool revealed nonlinear and interactive associations between several EMG features and subjective valence dynamics. These findings suggest that nonlinear ML models can better fit the relationship between subjective emotional valence dynamics and facial EMG than conventional linear models and highlight a nonlinear and complex relationship. The findings encourage emotion sensing using facial EMG and offer insight into the subjective-physiological association.