Scanning acoustic microscopy (SAM) has been applied successfully to measure leaky surface wave(LSAW) velocity from V(z) curve for material characterization. Besides LSAW, SAM produces a variety of wave modes in the material propagating with different phase speeds and features, one of which is the mode-converted ultrasound. In this paper, a novel method for simultaneous measurement of longitudinal and transverse acoustic wave velocities using the mode-converted ultrasound is developed and studied at SAM. Each ultrasound arriving at the acoustic lens with different speed and phase (or time-of-flight (TOF)) is measured by the defocused transducer to calculate longitudinal and transverse wave velocities. Simple mathematical ray analysis for the mode conversion is conducted to determine the relationship of acoustic velocities with TOF of the waves in plate. Experimental results for metals and glass show that the longitudinal and transverse wave velocities measured by the proposed method are as accurate as maximum 3% in error.