We theoretically revealed that a weak photoexcitation achieves the electric polarization-inversion with approximately 18% of all the charges, which was interpreted as a superimposition of multiexciton states, from the charge-ordered ferroelectric ground state of (TMTTF) 2 PF 6 at absolute zero temperature. Regarding a relative change of electric polarization (∆P/P ), the photoexcitation corresponds to 36%, which is much larger than ∆P/P of other typical organic materials. The value of ∆P/P ∼ 36% can be enlarged by a strong photoexcitation. This fact is useful not only for applications of this material and other analogous materials in optical devices but also for researches toward controlling electric polarizations by light, which is one of the recent attracting issues on photoinduced phase transition phenomena. The photoexcitation of ∆P/P ∼ 36% corresponds to the single peak of the optical conductivity in the low-energy region, which was also observed at 10 K. Theoretical calculations are based on a quarter-filled one-dimensional effective model with appropriate parameters and 50 unit cells.