We report the experimental and theoretical characterization of neutral Si(6)X(12) (X = Cl, Br) molecules that contain D(3d) distorted six-member silicon rings due to a pseudo-Jahn-Teller (PJT) effect. Calculations show that filling the intervenient molecular orbitals with electron pairs of adduct suppresses the PJT effect in Si(6)X(12), with the Si(6) ring becoming planar (D(6h)) upon complex formation. The stabilizing role of electrostatic and covalent interactions between positively charged silicon atoms and chlorine atoms of the subject [Si(6)Cl(14)](2-) dianionic complexes is discussed. The reaction of Si(6)Cl(12) with a Lewis base (e.g., Cl(-)) to give planar [Si(6)Cl(14)](2-) dianionic complexes presents an experimental proof that suppression of the PJT effect is an effective strategy in restoring high Si(6) ring symmetry. Additionally, the proposed pathway for the PJT suppression has been proved by the synthesis and characterization of novel compounds containing planar Si(6) ring, namely, [(n)Bu(4)N](2)[Si(6)Cl(12)I(2)], [(n)Bu(4)N](2)[Si(6)Br(14)], and [(n)Bu(4)N](2)[Si(6)Br(12)I(2)]. This work represents the first demonstration that PJT effect suppression is useful in the rational design of materials with novel properties.