The electron configuration of a series of low-spin (dicyano){meso-tetrakis(2,4,6-trialkylphenyl)porphyrinato}iron(III) complexes, [Fe(R-TPP)(CN)(2)](-) where R = Me, Et, or Pr-i, together with the parent [Fe(TPP)(CN)(2)](-), has been examined in dichloromethane-methanol solution by H-1 NMR, C-13 NMR, and EPR spectroscopies. While the ferric ion of [Fe(TPP)(CN)(2)](-) has shown a common (d(xy))(2)(d(xz),d(yz))(3) configuration, the ferric ions of the alkyl-substituted complexes [Fe(R-TPP)(CN)(2)](-) have exhibited the preference of a less common (d(xz),d(yz))(4)(d(xy))(1) configuration. Spectroscopic characteristics of the complexes in which ferric ions take the (d(xz),d(yz))(4)(d(xy))(1) configuration are (i) axial type EPR spectra, (ii) downfield shifted pyrrole and meta signals in H-1 NMR spectra, and (iii) downfield shifted meso-carbon signals in C-13 NMR spectra. Occurrence of the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) has been ascribed to the electronic interaction between iron (d(pi)) and cyanide (p(pi)*) orbitals. The interaction stabilizes the d(pi) orbitals and induces (d(xz),d(yz))(4)(d(xy))(1) configuration. Since the electron configuration of (dicyano){meso-tetrakis(2,6-dichlorophenyl)porphyrinato}iron(III), [Fe(Cl-TPP)(CN)(2)](-), which carries bulky electronegative chlorine atoms at the ortho positions, is presented as a common (d(xy))(2)(d(xz),d(yz))(3), the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) can be ascribed, at least partially, to the electron-donating ability of the meso-aryl groups.