In both organic and polymer synthesis, photochemistry of charge transfer complexes (CTCs) is considered as a powerful approach to expand visible‐light‐driven radical chemistry reaction. One reports herein on the development of a class of useful CTCs using pyridinium salts as efficient electron acceptors (combined with N, N, 3,5‐tetramethylaniline, TMA) to achieve a multiwavelength (375–560 nm) metal‐free LED photopolymerization process under mild conditions (open to air, without monomer purification and inhibitor removal). The UV–vis absorption spectra and molecular modeling simultaneously verify its potential blue‐green absorbing wavelength range. Also, their good thermal initiation behavior at relatively low temperatures makes it easier to achieve thick samples and/or polymerization in the shadow region in practice. More importantly, with excellent photoinitiating capability, the formulation is successfully applied to direct laser write (DLW) and high‐resolution 3D printing, yielding a series of objects with well‐defined structures, such as letters, ring, solid squares, and chess pieces. These new pyridinium salt acceptors further extend the applicability to visible photopolymerizable resins and additive‐containing formulations for efficient surface and deep curing.