Electronic MCD is used for the first time to obtain electronic and geometric structural insight into the free and DNA-bound states of the six-coordinate CoIII and VO2+ derivatives of 5,10,15,20-tetrakis(4-N-methylpyridyl)porphine. Correlations between MCD, CD, and optical spectra measured in the porphyrin Soret band (or B0) region, and FLDr literature data, are consistent with each metalloporphyrin having a face-on orientation in the major groove of CT DNA, sites 5‘AT3‘ and 5‘CG3‘ being preferred, and with porphyrin electric dipole transition moments (edtms) μex D (most perturbed direction in the bound porphyrin) and μex D (least perturbed) having orientation angles of α/β/β‘ = ∼45°/180°/90° and ∼45°/180°/270°, respectively.