Interface materials offer a means to achieve electrical control of ferrimagnetism at room temperature as was recently demonstrated in (LuFeO ) /(LuFe O ) superlattices. A challenge to understanding the inner workings of these complex magnetoelectric multiferroics is the multitude of distinct Fe centres and their associated environments. This is because macroscopic techniques characterize average responses rather than the role of individual iron centres. Here, we combine optical absorption, magnetic circular dichroism and first-principles calculations to uncover the origin of high-temperature magnetism in these superlattices and the charge-ordering pattern in the m = 3 member. In a significant conceptual advance, interface spectra establish how Lu-layer distortion selectively enhances the Fe  →  Fe charge-transfer contribution in the spin-up channel, strengthens the exchange interactions and increases the Curie temperature. Comparison of predicted and measured spectra also identifies a non-polar charge ordering arrangement in the LuFe O layer. This site-specific spectroscopic approach opens the door to understanding engineered materials with multiple metal centres and strong entanglement.