In the field of perovskite light-emitting diodes (PeLEDs), the performance of blue emissive electroluminescence devices lags behind the other counterparts due to the lack of fabrication methodology. Herein, we demonstrate the in situ fabrication of CsPbClBr2 nanocrystal films by using mixed ligands of 2-phenylethanamine bromide (PEABr) and 3,3-diphenylpropylamine bromide (DPPABr). PEABr dominates the formation of quasi-two-dimensional perovskites with small-n domains, while DPPABr induces the formation of large-n domains. Strong blue emission at 470 nm with a photoluminescence quantum yield up to 60% was obtained by mixing the two ligands due to the formation of a narrower quantum-well width distribution. Based on such films, efficient blue PeLEDs with a maximum external quantum efficiency of 8.8% were achieved at 473 nm. Furthermore, we illustrate that the use of dual-ligand with respective tendency of forming small-n and large-n domains is a versatile strategy to achieve narrow quantum-well width distribution for photoluminescence enhancement.