A　new　honeycomb-shaped　electroactive　metal-organic　framework　(MOF)　has　been　constructed　from　an　electron　deficient　naphthalenediimide　(NDI)　ligand　equipped　with　two　terminal　salicylic　acid　groups.　π-Intercalation　of　electron-rich　planar　tetrathiafulvalene　(TTF)　guests　between　the　NDI　ligands　stacked　along　the　walls　lowers　the　electronic　band　gap　of　the　material　by　ca.　1　eV.　An　improved　electron　delocalization　through　the　guest-mediated　π-donor/acceptor　stacks　is　attributed　to　the　diminished　band　gap　of　the　doped　material,　which　forecasts　an　improved　electrical　conductivity.　©　2017　American　Chemical　Society.