We present a photonics-based method of estimating Doppler frequency shift (DFS) and angle of arrival (AOA). The proposed identification method for the DFS and AOA is simultaneous and unambiguous. A reference radio frequency signal is introduced to realize the frequency downconversion. By monitoring the frequency of the downconverted signals generated after the photodetection, the direction ambiguity of the DFS is canceled out. The AOA can be instantaneously calculated through two downconverted signals via a Hilbert transform. Experimental results verify that a -77.90° to 77.90° AOA measurement with errors of less than ±1° is implemented, and a DFS measurement with errors of no more than ±3.1 Hz is also realized. Our proposed method not only removes the direction ambiguities of both DFS and AOA, but also avoids the dependence on echo signal power in AOA measurement, which largely increases the feasibility in realistic applications.