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Second phase precipitation plays a very important role in setting the properties of bainitic steels, which particularly rests with its responsibility for the initial failure of many materials. In the present work, Local field Electron Atom Probe (LEAP) investigations and High Resolution TEM analysis were performed in high carbon steel 100Cr6. Atom Probe analyses reveal the existence of cementite and ε-carbide in lower bainite. Cementite is found to be with a very small thickness (≈5 nm), comparing its length and width dimensions. The detection of ε-carbide in lower bainite implies a large excess of carbon trapped in bainitic ferrite when it first forms.