Four coumarin (2-oxo-2H-1-benzopyran) containing liquid crystalline polymethacrylates possessing the same monomer formula but different linkage directions and/or construction directions of their mesogens into the same main-chain were prepared and investigated. Each of the four polymers exhibits a smectic A liquid crystalline phase. The change of construction and/or linkage directions significantly affected their liquid crystalline properties. Especially, the change of the construction directions of the mesogens caused different photophysical and photochemical properties.