The unsaponifiable matters (UM) of chloroform-methanol, Soxhlet, enzyme-assisted aqueous and a rural aqueous extracted samples of shea fat were comparatively, separated by thin layer chromatography on Silica gel 60 plates. A band corresponding to a mixture of reference sterols, and another to lanosterol, of the Soxhlet extracted sample were eluted and analyzed by gas chromatography. The purpose was to investigate an earlier observation that the enzyme-assisted extracted samples had lower UM; and also to add to the otherwise scanty literature on shea fat unsaponifiables. The chloroform-methanol sample separated into 5 bands, compared to 3 apparent bands in each of the other samples. The bands had different color reactions with 50% H2SO4, and based on the reference standards, were distinguished into sterols, triterpene alcohols and hydrocarbons. The triterpene alcohols seemed to form the major components. The hydrocarbon fraction of the enzyme-assisted shea fat UM appeared to be significantly lesser than the others. Generally the observations suggested that the method of extraction could influence the UM of crude fats and oils. The sterol and triterpene alcohol fractions of the Soxhlet sample showed 6 and 5 major peaks respectively. Three sterols and two triterpene alcohols formed over 90% in each group. Based on the TLC and GC data, it appeared that cholesterol, β-sitosterol, campesterol, fucosterol, ergosterol or most of the common phytosterols are not apparently present in the shea fat unsaponifiables.