We herein report a new highly efficient green emissive hot-exciton molecule, 1,4-bis((4'-diphenylamino3-cyano-[1,1'-biphenyl]-4-yl)ethynyl)-2,5-bis(2-ethylhexyloxy)benzene (2EHO-TPA-CNPE) that consists of an extended D'-pi'-A-pi-D-pi-A-pi'-D' molecular p-system with diphenylamino end units (D') and ethynylene/phenylene spacers (pi/pi'). The new molecule exhibits high photoluminescence (PL) quantum efficiencies (Phi(PL) = 0.95 (solution) and 0.45 (spin-coated neat thin-film)), and a strong PL solvatochromic behavior revealing significant changes in excited state energies/characteristics (locally excited (LE) -> hybridized local and charge transfer (HLCT) - charge-transfer (CT)) depending on solvent polarity. Highly efficient (radiative exciton yield (eta(r)) = 50-59% >> 25%) green-emitting OLEDs were fabricated in a conventional device architecture by employing (non-)doped thin-films reaching a maximum current efficiency (CEmax) of 12.0 cd A(-1) and a maximum external quantum efficiency (EQE(max)) of 5.5%. The emission profile of the non-doped OLED has CIE 1976 (u', v') chromaticity coordinates of (0.10, 0.55) corresponding to a night vision imaging system (NVIS) compatible Green A region. 2EHO-TPA-CNPE-based OLED devices of industrial relevance were also fabricated by ink-jet printing the emissive layer and by fabricating an inverted architecture, which possessed respectable device performances of 2.4-6.1 cd A(-1). The solid-state solvation effect in OLED devices yields HLCT electronic behavior resulting in high Zr's, which is confirmed by TDDFT to originate from energetically/spatially favorable reverse intersystem crossings (RISCs) (T-2/3 -> S-1). As a unique observation, delayed fluorescence due to this RISC was evident in the PL decay lifetime measurement with a ns-scale lifetime of similar to 10 ns. These results clearly allow a better understanding of the structure-photophysical property-electroluminescence relationships in this new class of oligo(p-phenyleneethynylene)-based hot-exciton molecules, and it could open up new opportunities for high-performance solution-processed optoelectronic/sensing applications.