Crystal　needles　of　N,N-bis(1-ethylpropyl)-3,4,9,10-perylenebis(dicarboximide)　(EPPTC)　are　produced　through　p-stacking　and　are　embedded　in　the　thin　film　of　poly(9,9-din-hexylfluorenyl-2,7-diyl)　(PFO)　when　the　blend　solution　of　EPPTC　and　PFO　in　p-xylene　is　spin-coated　onto　a　glass　substrate.　Charge　transfer　(CT)　complex　is　resolved　from　the　spectroscopic　response　of　the　blend　film,　which　is　generated　only　when　the　PFO　molecules　are　excited.　Thus,　the　PFO　molecules　are　specified　as　donors　and　the　H-aggregated　EPPTC　as　acceptors　in　the　formation　of　CT　state　(CTS).　The　emission　resulting　from　the　CTS　in　the　red　is　further　recognized　by　its　much　longer　lifetime　than　both　the　intrinsic　emission　of　the　individual　EPPTC　molecules　and　that　of　their　pure　aggregates.　Near-field　analysis　verifies　that　the　CTS　form　on　the　boundary　between　the　PFO　and　the　crystal　phases.　The　CT　exciton　forms　by　bounding　the　hole　left　on　HOMO　of　the　donor　(PFO)　and　the　indirectly　transferred　electron　to　the　H-aggregate　state　of　EPPTC,　which　transits　back　to　the　ground　state　by　emitting　a　photon　at　about　650　nm.　This　introduces　special　physics　in　the　heterojunctions　that　are　coupled　with　the　H-aggregates　and　mechanisms　important　for　the　design　of　organic　photovoltaic　devices.　(c)　2013　Wiley　Periodicals,　Inc.　J　Polym　Sci　Part　B:　Polym　Phys,　2013,　51,　749-755