Differential scanning calorimetry and X-ray diffraction experiments on the phase transformations of cyclohexane dispersed within an emulsifying medium (microsamples 1 μm3 in volume) are presented. The existence of a third metastable crystalline phase (denotedε) besides the already-known phases (two stable phases,α andγ, and two metastable phases,β andδ) is demonstrated. Interpretations of the succession of transformations between these different phases and with the liquid phase, either upon cooling or upon heating, are given.