Modular chromophoric systems with minimal electronic coupling between donor and acceptor moieties are well suited for establishing predictive relationships between molecular structure and excited-state properties. Here, we investigate the impact of naphthyl-based connectivity on the photophysics of phenoxazine-derived orthogonal donor-acceptor complexes. While compounds in this class are themselves interesting as potent organic photocatalysts useful for visible-light-driven organocatalyzed atom-transfer radical polymerization and small-molecule synthesis, many other systems (e.g., phenazine, phenothiazine, and acridinium) exploit charge-transfer excited states involving a naphthyl substituent. Therefore, aided by the facile tunability of the phenoxazine architecture, we aim to provide mechanistic insight into the effects of naphthyl connectivity that can help inform the understanding of other systems. We do so by employing time-resolved and steady-state spectroscopies, cyclic voltammetry, and temperature-dependent studies on two chemical series of phenoxazine compounds. In the first series (N-aryl 3,7-dibiphenyl phenoxazine), we find high sensitivity of photophysical behavior to naphthyl connectivity at its 1 versus 2 positions, including a drop in the intersystem-crossing yield (Phi(ISC)) from 0.91 (N-1-naphthyl) to 0.54 (N-2-naphthyl), which we attribute to the establishment of an excited-state equilibrium in the singlet manifold. Drawing on the synthetic tunability afforded by phenoxazine, a modified series (N-aryl 3,7-diphenyl phenoxazine) is chosen to circumvent this equilibrium, thereby isolating the impact of naphthyl connectivity on charge-transfer energy and triplet formation. We conclude that donor-acceptor distance is a key design parameter that influences a host of excited-state and dynamical properties and can have an outsized impact on photochemical function.