In this work, three orthogonally bonded phenanthroimidazole based donor-acceptor (D-A) structured blue-emissive materials N-SBPMCN, N-ABPMCN and N-TBPMCN with different donor moieties are designed synthesized. Theoretical combined experimental researches proved that the involving of weak donor (spiro-fluorene and anthracene) and strong donor triphenylamine can form different locally-emissive (LE) dominated hybrid local and charge-transfer (HLCT) excited state, which can contribute to their high photoluminescent quantum yield (PLQY), satisfied electroluminescence performance and blue purity. Specifically, N-TBPMCN with strong donor triphenylamine that possesses more CT excited state components demonstrates the best electroluminescence performance and blue purity among the three materials, revealing that the molecular design of orthogonal D-A structure is of great potential in blue-emissive functional materials. Additionally, we also discovered that intermolecular CT state can also contribute to high exciton utilization.