This paper proposes a method of estimating the underwater acoustic direction-of-arrival using several laser beams impinging on a propagating underwater acoustic wave. The deflection of the laser beam caused by the spatial variation of the optical refractive index, which is further due to the modulation of the acoustic wave, reflects the information of direction-of-arrival and is sensed by the position sensitive detector (PSD). The sensing of the minute displacement on the PSD, in fact, introduces an extra dimension in the depth direction, which is a significant advantage over the conventional piezoelectric sensing regime. The employment of the extra sensing dimension can overcome several shortcomings, represented by spatial aliasing and phase ambiguity, existing in the current direction-of-arrival estimating methods. In addition, the ringing phenomenon of the piezoelectric effect is greatly reduced in the proposed laser-based sensing regime. By the flexibility of placing the laser beams, a prototype of the hydrophone is designed and manufactured, and a series of testing is performed. The results show that, benefiting from the probe beam deflection technique and combining the rough estimate and fine calculation, the resolution of the underwater acoustic direction-of-arrival can be improved to better than 0.016°, which can support and reform many underwater applications such as underwater acoustic communication, underwater detection, and ocean monitoring.