Organic　chromic　materials　with　photochromic　and　electrochromic　properties　are　promising　materials　for　photoelectric　applications.　Despite　some　reports　indicating　the　presence　of　these　properties　in　aromatic　imide　derivatives,　the　advancement　of　their　enduring　discoloration　performance　remains　an　unresolved　challenge.　Herein,　we　incorporated　of　charge-assisted　anion-π　interactions　into　aromatic　imide　derivatives　as　a　strategy　for　improving　the　stability　of　generated　free-radical,　and　a　series　of　pyridinium-annelated　perylene　diimides　salts　(PAPDI-X,　X　=　I−,　Br−,　Cl−,　NO3−,　PF6−)　were　synthesized.　With　variations　in　the　electron-donating　capabilities　(Lewis　basicity)　of　the　anions,　the　nature　of　anion-PDI　interactions　undergoes　a　transition　from　non-chromogenic　anion-π　interaction　to　chromogenic　anion-induced　electron　transfer　(ET)　phenomenon,　and　these　interactions　have　been　fully　characterized　by　UV/Vis,　NMR,　and　EPR　spectroscopies.　Among　the　evaluated　anions,　Br-　anion　with　moderate　Lewis　basicity　participates　in　ET　with　PAPDI　by　light　or　voltage　stimuli,　and　generate　stable　PAPDI-Br•−　radical　anion　and　PAPDI-Br2-　dianion　in　aprotic　solvent　or　in　solid　state,　thus　making　PAPDI-Br　exhibit　distinctive　photo/electrochromic　dual　responsive　behavior　based　on　radical　formation.　This　meaningful　design　provides　new　concepts　for　the　design　of　organic　chromic　materials　and　shows　great　prospects　in　optoelectrical　materials.　©　2023　Elsevier　Ltd