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A novel series of kinked star‐shaped oligofluorene/triazatruxene hybrids are conveniently prepared via a powerful microwave‐enhanced multiple coupling methodology. Constructing kinked star‐shaped architectures can effectively suppress crystallization and aggregation. The resulting materials are highly amorphous, showing stable amorphous morphology against crystallization. A triazatruxene core endows the materials with elevated highest occupied molecular orbital (HOMO) levels that are well matched to the anode work function, leading to a significantly improved hole‐injection property. They hybrids are highly luminescent in both solution (quantum yield is 0.52–0.80) and the solid‐state (quantum yield is 0.45–0.76) with bright blue emission. Remarkably, solution‐processed devices displaying single‐layer electroluminescence (EL) based on these oligomers exhibit efficient blue EL and demonstrate …