A ferroelectric transition of phenazine (Phz) chloranilic acid (H 2 ca) co-crystal was studied by 35 Cl nuclear quadrupole resonance (NQR). The single NQR line observed at 36.689MHz at 295K, split into a doublet below the ferroelectric transition temperature T c =253K in accord with the inversion-symmetry breaking at the H 2 ca molecular center in the crystal. The continuous variation of the splitting-width through T c suggests a second-order nature of this phase transition. The NQR frequency is consistent with the crystal structure in which the two acid hydrogen atoms of H 2 ca remain as attached to the quinone molecules. The spin-lattice relaxation time T 1 showed a decrease with decreasing temperature in the ferroelectric phase. This suggests the existence of a fast motion of nearby atomic group, which is a cause of electric field gradient fluctuation.