In an organic electroluminescent (EL) device, the recombination of injected holes and electrons produces what appears to be an ion-pair or charge-transfer (CT) exciton, and this CT exciton decays to produce one photon directly, or relaxes to a low-lying local exciton (LE). Thus the full utilization of both the energy of the CT exciton and the LE should be a pathway for obtaining high-efficiency EL. Here, a twisting donor-acceptor (D-A) triphenylamine-imidazol molecule, TPA-PPI, is reported: its synthesis, photophysics, and EL performance. Prepared by a manageable, one-pot cyclizing reaction, TPA-PPI exhibits deep-blue emission with high quantum yields (90%) both in solution and in the solid state. Fluorescent solvatochromic experiments for TPA-PPI solutions show a red-shift of 57 nm (3032 cm-1) from low-polarity hexane (406 nm) to high-polarity acetonitrile (463 nm), accompanied by the gradual disappearance of the vibrational band in the spectra with increased solvent polarity. The photophysical investigation and DFT analysis suggest an intercrossed CT and LE excited state of the TPA-PPI, originating from its twisting D-A configuration. This is a rare instance that a CT-state material shows highly efficient deep-blue emission. EL characterization demonstrates that, as a deep-blue emitter with CIE coordinates of (0.15, 0.11), the performance of a TPA-PPI-based device is rather excellent, displaying a maximum current efficiency of >5.0 cd A-1, and a maximum external quantum efficiency of >5.0%, corresponding to a maximum internal quantum efficiency of >25%. The effective utilization of the excitation energy arising from materials with intercrossed-excited-state (LE and CT) characters is thought to be beneficial for the improved efficiency of EL devices.