Density functional theory and finite field FF method were employed to investigate the fluoroalkyl chain containing biphenylester liquid crystal molecules, and the results showed that the lowest-energy excitation was obtained from HOMO to LUMO with p → p* transition, and the absorption wavelength was obtained at around 390 nm, belonging to the near UV absorption area. It is found that the title compound molecules display good nonlinear optical properties, and the values of the second- and third- non-linear optical properties are 35 × 10^-30 and 32 × 10^-35 esu, respectively.