To study structure-mesomorphism relationships of chiral materials based on menthol, a series of chiral compounds containing menthyl group were synthesized. Their chemical structures, formula, and the purity were characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance (H-1 NMR), and elemental analyses. The corresponding phase behavior was investigated with differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The effect of the mesogenic core, flexible spacer, and terminal groups on the mesophase formation and type was discussed. The compound 4-menthyloxyacetoxybenzoyloxy-4- (6-bromohexyloxy)biphenyl showed the smectic A (S-A) and cholesteric phases on heating cycle, and a cubic Blue Phase, chiral smectic C (S-C(*)), S-A and cholesteric phases on cooling cycle. However, the compound 4-menthyloxyacetoxybenzoyloxy-4-(4-bromobutoxy)biphenyl showed enantiotropic S-C(*), S-A and cholesteric phases, moreover, the platelet texture of a cubic Blue Phase was also observed on cooling cycle. The methacrylate monomer with six flexible methylene units and three phenyl rings as mesogenic core only showed cholesteric phase, while the methacrylate monomer with four methylene unit and three phenyl rings showed the S-C(*) and cholesteric phases. However, when the terminal methacryloyloxy groups in the monomers were substituted by thiophenylacryloyloxy groups, the corresponding monomers all show no mesophase. With increasing the rigidity of mesogenic core or decreasing the flexible methylene spacer length, the corresponding melting temperature (T-m) or isotropic temperature (T-i) increased.