Electro-optic (EO) devices with high EO coefficients at radio and microwave frequencies are integral components of the photonics industry. This work determines the EO effect of ferroelectric Li-doped niobium-rich potassium tantalate niobate (K0.95Li0.05Ta1-xNbxO3; KLTN) single crystals using improved dynamic EO measurement. The phase transitions of KLTN crystals were investigated via variable-temperature Raman spectroscopy. A full view of the surface displacement and velocity for the KLTN sample at the resonant frequency was studied using an ultra-frequency vibrometer. The KLTN sample with x = 0.60 exhibits the enhanced effective EO coefficient (gamma(e)) similar to 217 pm/V near the piezoelectric resonant peaks, which is comparable with the value at low frequency. The piezoelectric enhanced EO property of KLTN single crystals can be attributed to nonlinear polarization and nonzero stress, and showing promising for designing practical optical-piezoelectric-mechanism coupling devices.