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.　©　2022　Wiley-VCH　GmbH.