In this report, we describe a modular synthesis approach towards a new series of non‐centrosymmetric, dipolar 4,4′‐bipyridines bearing 2,6‐ and 3,5‐functionalized pyridyl moieties at the peripheries. Central to our strategy is the selective substitution on only one pyridyl motif that could contain electron‐donating (−CH3) or electron‐withdrawing (−F, −Cl, −CF3) groups which causes electronic/steric effects on one nitrogen atom in 4,4′‐bipyridines. This synthetic protocol was further applied to prepare azo‐functionalized (−N=N−) asymmetric bipyridines and non‐centrosymmetric 4,4′‐bipyridine N‐oxide scaffolds, which overcome the synthetic hurdles oxidizing 4,4′‐bipyridines to N‐monoxides selectively at only one pyridine. Compared to the conventional symmetrical bipyridines, the dipolar non‐centrosymmetric molecular tectons pave the way for the realization of non‐centrosymmetric supramolecular assemblies because of the difference in the binding energy of the pyridyl nitrogen atoms.