The thermoelectric properties of the n-type semiconductor TiNiSn were optimized by partial substitution with metallic MnNiSb in the half Heusler structure. Herein, we study the transport properties and intrinsic phase separation in the Ti1-xMnxNiSn1-xSbx system. The alloys were prepared by arc-melting and annealed at temperatures obtained from differential thermal analysis and differential scanning calorimetry results. The phases were characterized using powder X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and differential scanning calorimetry. After annealing, the majority phase was TiNiSn with some Ni-rich sites, and the minority phases were primarily Ti6Sn5, Sn and MnSn2. The Ni-rich sites were caused by Frenkel defects; this led to metal-like behavior in the semiconductor specimens at low temperature. For x ≤ 0.05 the samples showed an activated conduction, whereas for x > 0.05 they showed metallic character. The figure of merit for x = 0.05 was increased by 61% (zT = 0.45) in comparison with the pure TiNiSn.