An alkali-metal-doped effect on the nonlinear optical (NLO) property in new electrides is studied. The electrides are formed by doping alkali atom Li into a fluorocarbon chain H-(CF2-CH2)(3)-H. Six stable structures of the Li-n-H-(CF2-CH2)(3)-H (n = 1, 2) complexes with all real frequencies are obtained at the MP2/6-31+G (d) level. Among these six structures, the largest first static hyperpolarizabilities (beta(0)) are found to be 76 978 au, which is much larger than the beta(0) value of 112 au for H-(CF2-CH2)(3)-H. Clearly, the Li-atom-doped effect on the first hyperpolarizability is dramatic. Three interesting relationships between the structure and beta(0) value have been observed. (1) For the one-Li-atom-doped systems as well as for the structures with two opposite Li atoms, the shorter the distance between the Li atom and difluoromethyl group, the larger the beta(0) value. (2) The beta(0) values of the two-Li-atom-doped chains are much larger than those of the one-Li-atom-doped systems, except for the case of cis-AB where the Li-Li distance (2.847 A) is close to the bond length of the Li-2 molecule (2.672 A). (3) For the two-Li-atom-doped chains, the beta(0) value increases as the Li-Li distance increases. These relationships between the structure and beta(0) value may be beneficial to experimentalists for designing electrides with large NLO responses by using the alkali-metal-doped effect.