We theorize that political values express basic personal values in the domain of politics. We test a set of hypotheses that specify how the motivational structure of basic values constrains and gives coherence to core political values. We also test the hypothesis that core political values mediate relations of basic personal values to voting demonstrated in previous research. We measured the basic personal values, core political values, and vote of Italian adults both before (n = 1699) and after (n = 1030) the 2006 national election. Basic values explained substantial variance in each of eight political values (22% to 53%) and predicted voting significantly. Correlations and an MDS projection of relations among basic values and political values supported the hypothesized coherent structuring of core political values by basic values. Core political values fully mediated relations of basic values to voting, supporting a basic values—political values—voting causal hierarchy.