In recent years, multi-label emotions of user tweets have beenexplored to identify user opinion, sentiment, stance, and preferences.Many studies and datasets are available to identify and analyze useremotions. Most benchmark corpora designed for user emotion analysisinclude news websites, blogs and user tweets. However, there is little exploration of political emotions in the Indian context for multi-label emotion classification problems. This paper presents the PoliEMO dataset -a novel benchmark corpus of political tweets in a multi-label setup forIndian elections, consisting of over 3.5K tweets annotated manually. Wegenerate 6,792 labels of six emotion categories: anger, insult, joy, neutral,sadness, and shameful. We utilize the PoliEMO dataset to understandemotions in a multi-label context using state-of-the-art machine learning algorithms with multi-label classifier (BR,CC, LP, MkNN with GBand LR), deep learning (CNN, LSTM and Bi-LSTM) and transformerbased method (BERT). Our experiments show Bi-LSTM outperformswith micro-averaged F1-score of 83%, macro-averaged F1-score of 78%,and accuracy 68% as compared to state-of-the-art approaches.