Mesogen‐jacketed liquid crystalline polymers (MJLCPs) with both electron‐transport oxadiazole and hole‐transport thiophene in the side chain were reported for their promising electroluminescent property. Monomers of 2,5‐bis5‐[(4‐alkoxyphenyl)‐1,3,4‐oxadiazole]thiophen‐2‐yl}styrene (M‐Cm, m is the number of the carbons in the alkoxy groups, m = 8,10) were synthesized and confirmed by 1H‐NMR, mass spectrometry