To our knowledge, prior work on ladder-type molecules with rigid backbones and -SMe anchors has not reported the well-defined conductance features observed here. Rigid molecular backbones generally show minimized structural variations compared to flexible molecular backbones. However, the ladder-type molecules studied here contain terminal anchor -SMe groups, which retain rotational degrees of freedom. We hypothesize that a donor-acceptor (D-A) interaction between electron-deficient backbones and electron-rich -SMe anchors constrains anchor rotation by favoring specific angles , thus reducing variability in junction conductance. To test this hypothesis, we performed DFT calculations on a hypothetical neutral analog molecule L1-neutral complemented by a dihedral angle sweep. The energy barrier for bond rotation in L1-neutral is approximately 3 kT, but the barrier increases substantially to >7 kT for L1-PF6. We further investigated the frontier orbitals corresponding to the dihedral angles at the highest and the lowest energies. In the case of L1-PF6 (Supplementary Figs. 77), as the bond undergoes rotation from the lowest to the highest energy structure, a notable decrease in HOMO orbital overlap was observed between the -SMe anchor and the backbone. This observation implies that the anchor group engages in electron delocalization only at specific dihedral angles, subsequently restricting the rotational degrees of freedom. In contrast, L1-neutral (Supplementary Figs. Our work presents a new molecular design strategy for molecular electronics that provides promising new avenues for overcoming challenges associated with fabrication of nanoscale devices with precise gap dimensions. Using a unique one-pot multicomponent synthesis strategy, we created a diverse range of positively charged ladder molecules from readily available starting materials. Our results show that charged ladder molecules exhibit exceptional shape-persistent conductance behavior in molecular junctions, regardless of pendant substituent groups, counter anions, or junction displacement. This conductance behavior arises from both the rigidity of the ladder backbone and the constrained rotation of the anchor in charged systems. Furthermore, the ladder structure promotes electron delocalization, enhancing conductance up to extremely high levels (~10 1.6 G0) compared to non-ladder counterparts. Interestingly, we further show that the probability of different binding sites can be controlled by varying the applied bias, which demonstrates control over dual charge transport pathways as a function of applied voltage. Overall, the innovative synthetic strategies and molecular design principles presented in this work highlight the role of charged laddertype molecules as promising candidates for next-generation materials in the quest for miniaturization in electronic devices.