In the previous study, the existence of an unidentified ferroelectric smectic phase is demonstrated in the low‐temperature region of the ferroelectric smectic A phase, where the layer spacing decreases with decreasing temperature. In the present study, the phase is identified by taking 2D X‐ray diffraction images of a magnetically oriented sample while allowing it to rotate and constructed a 3D reciprocal space with the sample rotation angle as the third axis for the whole picture of the reciprocal lattice vectors originating from the smectic structure. Consequently, circular diffraction images are obtained when the reciprocal lattice vectors are evenly distributed on the conical surface at a certain inclination angle in the reciprocal space. This result provides clear evidence that the phase in question is smectic C. The polarization properties also showed that the observed smectic C phase has spontaneous polarization in the direction parallel to the director and is identified as ferroelectric smectic C. These results provide a new type of classification for liquid crystalline phases that has been established over many years and is a significant contribution to the basic science of soft matter research.