The effect of Ti microalloying on the precipitation of NbC particles in Nb-microalloyed and Nb-Ti-microalloyed steels was investigated by scanning transmission electron microscopy. The experimental results illustrate that NbC precipitates tend to be formed via a conventional “nucleation and growth” mechanism in Ti-free steel, while the particles would be precipitated as a complex form of TiN cuboid core and NbC hemispherical cap in Ti-Nb-microalloyed steel with 0.009 wt.% Ti and 0.0046 wt.% N. Ti microalloying contributed to the refinement of the precipitate size, and an enhancement of the volume fraction of NbC particles was also found based on the experimental observations.