The work characterizes the unsaponifiable matter of fats released in pitting green (GP) and ripe (RP) olives, in pitting/stuffing green olives with vegetable (GPSV) and animal (GPSA) products and in the fat settled at the end of the factory sewer system (W). The unsaponifiable matter ranged from 1.94% (RP) to 5.91% (GPSA); total sterols from 1319 mg/kg fat (GPSV) to 2002 mg/kg fat (RP), with β-sitosterol as the most abundant. Fatty alcohols ranged from 242 mg/kg (GP) to 556 mg/kg (W), with C22 as the most abundant. Triterpene diols were found only in GPSV (erythrodiol + uvaol, 0.80%). Wax was not present in the fats from GP and RP but increased with the general fat degradation in the order GPSV (128 mg/kg), GPSA (171 mg/kg) and W (263 mg/kg). Chemometric analysis was able to detect differences among the diverse fats; sterols + fatty alcohols cluster analysis was useful for fat grouping.