In this article, the problem of simultaneously estimating and localizing multiple-input multiple-output (MIMO) radar emitters is considered for a distributed multi-station passive localization system, wherein the transmitted signal is unknown for receiver stations. To achieve highly accurate and robust localization performance, a novel algorithm based on the direct position determination (DPD) algorithm, Karhunen–Loève (KL) transform, and feature matching (FM) is addressed to jointly estimate the emitter position and the unknown signal waveform. First, we further derive the objective function of the DPD method and present an enhanced strategy to exploit as much waveform information as possible without any prior knowledge. By applying KL transform and FM techniques, the proposed method achieves MIMO radar emitter identification and emitter localization. The numerical results show that the proposed algorithm outperforms the existing DPD approaches which ignore the transmitted signals, especially for a low signal-to-noise ratio (SNR).