Thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) are known to occur in organic D–A–D and D–A systems where the donor group contains the phenothiazine unit and the acceptor is dibenzothiophene-S,S-dioxide. This study reports the synthesis and characterization of one new D–A and four new D–A–D systems with methoxy groups on the phenothiazine to examine their effect on emission properties in the zeonex matrix. X-ray analysis and highly specialized NMR techniques were used to characterize asymmetric methoxy-substituted derivative 3b, which is chiral at N because of an extremely high flipping barrier at the phenothiazine N atom. Based on hybrid-density functional theory computations, the methoxy substituents tune the relative stabilities of the axial conformers with respect to equatorial conformers of the phenothiazine units, depending on their substitution position. This conformational effect significantly influences both TADF and RTP contributions compared to the parent D–A–D system. It is also demonstrated that the equatorial forms of D–A–D and D–A systems in zeonex exhibit TADF. Additionally, the methoxy groups promote luminescence in D–A–D systems where only axial conformers exist. This work reveals further design opportunities for more efficient TADF and RTP molecules.