We have studied the molecular orientation by the phase transitions of the chiral smectic liquid crystals, 4-(1-Trifluoromethyl-6-ethoxy-hexyloxycarbonlphenyl)-4-nonyloxybiphenyl-4-carbo-xylate (R-TFMEOHPNBC) to seek the original solution of the zig-zag defect using two different experimental techniques; optical system and x-ray scattering. The phase sequence is gamma ferroelectric (SmCγ ∗) → smectic A (SmA) → isotropic (I). Existence of two layer spacing at chiral smectic phase gives a possibility of the molecular orientation in two different tilt angles, θ1 and θ2 , which are separated each other to the layer normal at a given temperature. The gamma ferroelectric-like phase is, first, discovered in the single compound.