The Doppler scatterometer is a new style of remote sensing tool that can provide current measurements over a wide swath for rapid global coverage. The existing current estimation method for Doppler scatterometry uses the maximum likelihood method to jointly derive the wind and current fields but shows high computational complexity. Moreover, the current radial speeds measured along two arbitrary observation azimuths are used to derive the vector current according to the parallelogram rule, which is not applicable for the case where two observation azimuths are not perpendicular. In this paper, a vector current velocity inversion method using an optimally selected observation azimuth combination—as well as a general current velocity calculation method—is proposed for Doppler scatterometry. Firstly, current radial speeds along several different observation azimuths are estimated using an interferometric phase difference matching method with low computational complexity. Then, two current radial components of each point are arbitrarily selected to estimate a preliminary current direction using the proposed vector current velocity derivation method. Finally, two observation azimuths that have the smallest intersection angles with the preliminarily estimated current direction are selected for vector current velocity determination. With the Ocean Surface Current Analyses Real-time (OSCAR) data as current input, vector current estimation experiments were conducted based on simulation analysis using an instrument conceptual design model for a pencil-beam scatterometer. The results show that the standard deviation of the estimated current velocity magnitude is 0.06 m/s. Compared with the reported results obtained by the existing method, the inversion accuracy of velocity magnitude is improved by 67%.