Modern mate selection theories suggest that people are more likely to marry someone similar to themselves in terms of numerous attributes. Recent research has demonstrated a positive relationship between marital satisfaction and inter-subject correlation (ISC) of neural responses while viewing movies in married couples. Nevertheless, conventional ISC methods solely capture information about similarity in the temporal evolution of region-averaged neural responses, disregarding nuanced spatially distributed response topographies. Here, we integrated ISC and multi-voxel pattern (MVP) analysis to capitalize inter-subject trajectory similarity (ISTS) of MVP. We demonstrated that married couples showed significantly higher ISTS than randomly selected pairs, during movie viewing and resting state. The ISTS was particularly positively associated with marital satisfaction in married couples while viewing movies. In order to investigate latent “psychological states” characterized by relatively stable patterns of MVP, a hidden Markov model was used to segment the neural events in married couples during viewing movies. We found the ISTS within manually defined events was a strong predictor of marital satisfaction. These results suggest that married couples with high-level marital satisfaction may experience similar trajectories of mental states when exposed to a common marital-related stimulus, and extend our understanding of the neurobiological signatures of intimate relationship.