Understanding complex emotions, characterized by the co-occurrence of positive and negative feelings, is crucial for unlocking the full spectrum of human affective experiences. However, the behavior and neural representation of ambivalent feelings, particularly during awe, remain elusive. To address this gap, we combined awe-inducing virtual reality clips, electroencephalogram, and a deep learning-based dimensionality reduction technique (N= 43). Behaviorally, awe ratings were precisely predicted by the duration and intensity of ambivalent feelings, not by single valence metrics. In the electrophysiological analysis, we identified participant- and clip-specific latent neural spaces sharing valence representation structures across individuals and stimuli. In these spaces, ambivalent feelings during awe were distinctly represented, and the variability in their distinctiveness specifically predicted awe ratings. Additionally, frontal delta oscillations mainly engaged in differentiating valence representations. Our findings demonstrate that awe is fundamentally an ambivalent experience reflected in both behavior and distinct patterns of electrophysiological activity. This work provides a new framework for understanding complex emotions and their neural underpinnings, with potential implications for affective neuroscience and mental health research.