Frequency diverse array (FDA) offers potential applications for joint range and angle estimation, but ambiguous estimates may be generated due to its range-angle coupling and time-variant beampattern. This problem can be addressed by jointly utilizing FDA and multiple-input multiple-output (MIMO) radar, but only multiple signal classification (MUSIC) algorithm was considered in the FDA literature. In order to avoid high computational complexity in the MUSIC algorithm due to the required 2-D peak searching, in this paper, we propose a two-stage estimating signal parameters via rotation invariance technique (ESPRIT) algorithm for FDA-MIMO radar to estimate both range and angle of targets, along with the proposed pairing method for unambiguous estimates. Moreover, closed-form expressions of the mean squared error (MSE) and Cramér-Rao lower bound (CRLB) for angle and range estimations are also derived. All proposed methods and derivations are verified by both theoretical analysis and numerical results, which show the superiority of FDA-MIMO radar over conventional phased-array radar and MIMO radar in target localization.