In this letter we report the nonlinear property of pyrylium-doped superpolymer studied by degenerate four-wave mixing (DFWM). The nonlinear susceptibility x(3) of pyrylium-doped polymer is 3×10-10 e.s.u.. The time resolution curve formed by the decay of phase conjugate reflection as a function of the delay of the backward pump pulse in the counterpropagating DFWM scheme was observed, and the relaxation time is 30 ps. The electronic and brientational mechanisms are discussed.