Abstract Herein, we report two hybrid zero‐dimensional (0D) lead‐free metal oxide halides of [PPip]Sb 2 Cl 6 O ( 1 ) ([PPip]=1‐(2‐Pyridyl)piperazine) and [PmPip]Sb 2 Cl 6 O ( 2 ) ([PmPip]=1‐(2‐Pyrimidyl)piperazine). Compounds 1 and 2 are able to exhibit narrow blue light emissions excited by UV light with photo‐luminescence quantum yields (PLQYs) of 25.49 % and 24.71 %, respectively. Through systematical characterizations, these blue light emissions can be attributed to the radiative transition in conjugated organic cations. Benefiting from the highly efficient intrinsic blue emissions, compound 2 can be used as blue fluorophor to fabricate liquid crystal display. This work provides a new to assembly blue emitter through by virtue of the optical active organic cations in hybrid materials.