The two most important magmatic differentiation series on Earth are the Fe-enriching tholeiitic series, which dominates the oceanic crust and island arcs, and the Fe-depleting calc-alkaline series, which dominates the continental crust and continental arcs. It is well known that calc-alkaline magmas are more oxidized when they erupt and are preferentially found in regions of thick crust, but why these quantities should be related remains unexplained. We use the redox-sensitive behavior of europium (Eu) in deep-seated, plagioclase-free arc cumulates to directly constrain the redox evolution of arc magmas at depth. Primitive arc cumulates have negative Eu anomalies, which, in the absence of plagioclase, can only be explained by Eu being partly reduced. We show that primitive arc magmas begin with low oxygen fugacities, similar to that of mid-ocean ridge basalts, but increase in oxygen fugacity by over two orders of magnitude during magmatic differentiation. This intracrustal oxidation is attended by Fe depletion coupled with fractionation of Fe-rich garnet. We conclude that garnet fractionation, owing to its preference for ferrous over ferric iron, results in simultaneous oxidation and Fe depletion of the magma. Favored at high pressure and water content, garnet fractionation explains the correlation between crustal thickness, oxygen fugacity, and the calc-alkaline character of arc magmas.