In this paper, a photonic-assisted system for simultaneous and unambiguous measurement of the Doppler frequency shift (DFS) and angle-of-arrival (AOA) using a dual-parallel dual-drive Mach–Zehnder modulator (DP-DDMZM) is proposed and investigated. The echo signals received by two receiving antennas are applied to the radio frequency ports of one sub-DDMZM of the DP-DDMZM. The bias port of the sub-DDMZM is fed by a binary electrical signal that is used to construct two different mapping curves on the relationship between the phase difference and the power of the output intermediate frequency (IF) signal. Therefore, unambiguous AOA measurement with extended range can be realized. The transmitted signal is input into the other sub-DDMZM to implement single-sideband modulation, which is then frequency shifted based on serrodyne modulation. Both the value and direction of DFS can be derived intuitively from the frequency of the output IF signal. Simulation results show that the measurement error of unambiguous DFS measurement is no more than ±0.008Hz in the range of −100kHz to 100 kHz, and the measurement error of unambiguous AOA is less than ±0.2∘ in the range of −70.8∘ to 70.8°. Moreover, since the scheme does not involve the construction of multi-channels or use of any filter or polarization dependent device, the system has concise structure, high accuracy, large operating bandwidth, and strong robustness, and can be considered as a very promising solution for actual applications.