Three experiments examined the latent structure of values. Participants rated the importance of values clustered in pairs. Based on [Schwartz, S. H. (1992). Universals in the content and structure of values: Theoretical advances and empirical tests in 20 countries. In M. Zanna (Ed.), Advances in Experimental Social Psychology (Vol. 25, pp. 1–65). San Diego, CA: Academic Press.] circular model, we predicted and found that the time to rate the second value in each pair was shorter when the two values were motivationally congruent or opposing than when the two values were unrelated (Experiment 1). As expected, this was not the case when participants had to compare the importance of values within each pair (Experiment 2). Finally, semantic relatedness between values failed to explain the effects of motivational compatibility (Experiment 3). Taken together, these results reveal a coherent pattern of value relations driven by motivational compatibilities, over and above perceived semantic relatedness.