Photogenerated organic triplet–doublet systems have attracted an increasing amount of attention in recent years due to their versatility and suitability for a range of technological applications in the emerging field of molecular spintronics. Such systems are typically generated by enhanced intersystem crossing (EISC) preceded by photoexcitation of an organic chromophore covalently linked to a stable radical. After formation of the chromophore triplet state by EISC, triplet state and stable radical may interact, whereby the nature of the interaction depends on the exchange interactionJTRbetween them. IfJTRsurpasses all other magnetic interactions in the system, molecular quartet states may be formed by spin mixing. For the design of new spintronic materials based on photogenerated triplet–doublet systems, it is crucial to gain further knowledge about the factors influencing the EISC process and the yield of the subsequent quartet state formation. Here we investigate a series of three BODIPY–nitroxide dyads characterised by different separation distances and different relative orientations of the two spin centres. Our combined results from optical spectroscopy, transient electron paramagnetic resonance, and quantum chemical calculations suggest that the chromophore triplet formation by EISC is mediated by dipolar interactions and depends primarily on the distance between the chromophore and radical electrons, while the yield of the subsequent quartet state formation by triplet–doublet spin mixing is influenced by the absolute magnitude ofJTR.