High birefringence (Δn) and low melting point (Tm), high Δn and low rotational viscosity (γ1) are two pairs of contradictory performance parameters. In this work, two high-Δn LC diluters 3PTPF2V and 3PTPFOV are proposed to achieve a fine balance between them. These target compounds containing a rigid tolane core, a lateral fluorine substituent and a buty-3-enyl or allyloxy terminal group were further synthesized. Some experimental instruments, such as POM, DSC, Abbe refractometer, multi-channel liquid crystal evaluation system, were adopted to investigate their properties of mesomorphic phase behavior, Tm, Δn and γ1 by comparing with classical LC diluters 3HHV and V2PTP2V. Meanwhile, density functional theory (DFT) calculations were employed to correlate the experimental results, and their comprehensive effects on two high-Δn LC mixtures were further evaluated. Research results indicated that both target compounds possess low Tm (∼20 °C), low γ1 (∼6.5 mPa·s), and high Δn (>0.26). Performance in high-Δn LC mixture demonstrated that they could effectively decrease Tm and γ1, meanwhile maintain high Δn and Tc values, meaning their potential application prospects in fast-response LC optical devices.