Electrodermal activity (EDA) reflects sympathetic nervous system activity through sweating-related changes in skin conductance. Decomposition analysis is used to deconvolve the EDA into slow and fast varying tonic and phasic activity, respectively. In this study, we used machine learning models to compare the performance of two EDA decomposition algorithms to detect emotions such as amusing, boring, relaxing, and scary. The EDA data considered in this study were obtained from the publicly available Continuously Annotated Signals of Emotion (CASE) dataset. Initially, we pre-processed and deconvolved the EDA data into tonic and phasic components using decomposition methods such as cvxEDA and BayesianEDA. Further, 12 time-domain features were extracted from the phasic component of EDA data. Finally, we applied machine learning algorithms such as logistic regression (LR) and support vector machine (SVM), to evaluate the performance of the decomposition method. Our results imply that the BayesianEDA decomposition method outperforms the cvxEDA. The mean of the first derivative feature discriminated all the considered emotional pairs with high statistical significance (p<0.05). SVM was able to detect emotions better than the LR classifier. We achieved a 10-fold average classification accuracy, sensitivity, specificity, precision, and f1-score of 88.2%, 76.25%, 92.08%, 76.16%, and 76.15% respectively, using BayesianEDA and SVM classifiers. The proposed framework can be utilized to detect emotional states for the early diagnosis of psychological conditions. © 2023 European Federation for Medical Informatics (EFMI) and IOS Press.