This paper focuses on studies of surface leaky longitudinal waves (SLLWs) on LiNbO3 substrates. The theoretical results of searching SLLWs on LiNbO3 in the range of Euler angles (0 degrees, beta, 90 degrees) and (alpha, 0 degrees, 0 degrees are presented, which shows the velocity can be up to 6700 to 7300m/s nearly twice that of normal SAW and has attenuation in the order of 10(-4)dB/lambda, however very low piezoelectric coupling coefficient (no more than 0.14%) in the range of Euler angles(0 degrees, beta, 90 degrees). The theoretical results also show that SLLWs, in the range of Euler angles(alpha, 0 degrees, 0 degrees) of LiNbO3, have phase velocities 6500 to 7000m/s and relatively high piezoelectric coupling coefficient (up to 0.6%). The experimental results at the Euler angles(0 degrees, 38 degrees, 90 degrees) and (16 degrees, 0 degrees, 0 degrees) On LiNbO3 are also shown in this paper.