Facial attractiveness is closely related to romantic love. To understand if the neural underpinnings of perceived facial attractiveness and facial expression are similar constructs, we recorded neural signals using an event-related potential (ERP) methodology for 20 participants who were viewing faces with varied attractiveness and expressions. We found that attractiveness and expression were reflected by two early components, P2-lateral (P2l) and P2-medial (P2m), respectively; their interaction effect was reflected by LPP, a late component. The findings suggested that facial attractiveness and expression are first processed in parallel for discrimination between stimuli. After the initial processing, more attentional resources are allocated to the faces with the most positive or most negative valence in both the attractiveness and expression dimensions. The findings contribute to the theoretical model of face perception.