Objective and background: The present study tested whether the similarity levels of relationship-oriented values among Chinese couples would be higher than those among randomly matched male–female pairs. Furthermore, we examined whether couple similarity of relationship-oriented values would predict spouses’ marital satisfaction and life satisfaction above the actor and partner effects of relationship-oriented values over time and the potential marriage cohort differences. Method: Data were retrieved from the China Family Panel Studies data set in 2010–2014. Our study included a nationally representative sample of 10,860 first-married couples who provided data on relationship-oriented values, marital satisfaction, and life satisfaction. Results: The average profile similarity on relationship-oriented values of the real couples was higher than that of the randomly matched male–female pseudo couples. Actor–Partner Interdependence Model analyses showed that (1) couple similarity of relationship-oriented values was positively associated with husbands’ and wives’ life satisfaction indirectly through wives’ marital satisfaction among couples with short to medium marital duration, even after controlling for life satisfaction 4 years ago and a set of sociodemographic variables; (2) husbands’ relationship-oriented values were positively associated with couples’ life satisfaction indirectly through husbands’ marital satisfaction among couples with short to medium and long marital duration. Conclusion: With a large dyadic sample of Chinese couples, our findings expand the literature on the significant role of couple similarity of relationship-oriented values in personal and relational well-being.