MXene-transition metal dichalcogenide (TMD) heterostructures are synthesized through a one-step heat treatment of Nb2C and Nb4C3. These MXenes are used without delamination or any pre-treatment. Heat treatments accomplish the sacrificial transformation of these MXenes into TMD (NbS2) at 700 and 900 °C under H2S. This work investigates, for the first time, the role of starting MXene phase in the derivative morphology. It is shown that while treatment of Nb2C at 700 °C leads to the formation of pillar-like structures on the parent MXene, Nb4C3 produces nano-mosaic layered NbS2. At 900 °C, both MXene phases, of the same transition metal, fully convert into nano-mosaic layered NbS2 preserving the parent MXene's layered morphology. When tested as electrodes for hydrogen evolution reaction, Nb4C3-derived hybrids show better performance than Nb2C derivatives. The Nb4C3-derived heterostructure exhibits a low overpotential of 198 mV at 10 mA cm−2 and a Tafel slope of 122 mV dec−1, with good cycling stability in an acidic electrolyte.