Four groups of low transformation temperature (LTT) deposited metals with different Ni contents were prepared, and their microstructures were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and electron backscattered diffraction techniques. The relationship between the microstructures of the mixed martensite-retained austenite (RA) phases and their impact toughness were investigated; it was found that the impact toughness of the LTT deposited metals increased with increasing volume fraction of RA. In particular, its magnitude was higher for the specimens containing the lath martensite, interlath RA, and intercellular RA phases than for those composed of the lath martensite and interlath RA. The toughness of the lath martensite-RA mixed microstructure was primarily determined by the presence of the soft RA phase (containing film interlath RA and stringer intercellular RA), while lath martensite phase characterized by a high density of tangled dislocations and relatively small amount of twinned substructures resulted in the embrittlement of the LTT deposited metals. The dislocation absorption by the retained austenite and transformation-induced plasticity (TRIP) effects of RA were found to be main reasons for the improvement in materials toughness during crack initiation stage. The subsequent crack propagation proceeds via the TRIP and the transformation-induced crack termination mechanisms; it is also significantly affected by the increased fraction of martensite/RA boundaries. The optimization of the RA fraction in the martensite-RA dual structure is a potentially effective method for the toughness enhancement of the LTT deposited metals containing martensite-RA dual phases.