Emotions are processed asymmetrically by the human brain. Frontal alpha asymmetry (FAA) as measured by electroencephalographic (EEG) power in the alpha band (8–13 Hz), is a sensitive indicator of asymmetric brain activity in the frontal cortex. The current study aimed to analyze the frontal EEG asymmetries in terms of valence and motivational direction. We presented 37 participants with three film excerpts that were selected from the standard emotional film database to elicit three target emotions: tenderness, anger, and neutrality. Participants’ self-reports on their induced emotional responses and EEG signals were recorded and analyzed. The results showed that individuals displayed lower alpha power in the left hemisphere than the right hemisphere when they were watching a tender film, indicating that tenderness was positive and related to approach motivation. In contrast, when watching an angry movie, participants showed higher alpha power in the left hemisphere than the right hemisphere, suggesting that anger was negative and associated with withdrawal motivation. These findings help to link positive and approach-motivated tenderness with greater left hemispheric activation and state-anger with greater right hemispheric activation through the analysis of FAA.