Phytosterols occur in relatively high concentration in the seeds of rapeseed (Brassica napus L.) and in lower concentration in olive (Olea europaea L.) oil. The aim of this research was to investigate some new rapeseed varieties and olive genotypes that are grown in Northwest Turkey and to compare the phytosterol contents of both crops. For rapeseed, the data were collected in the growing seasons 2004–2005 from a field experiment with 19 new rapeseed varieties and three replications. For olives, 21 different varieties were used in the 2004–2005 and 2005–2006 growing seasons. The separation and identification of free phytosterols and the analysis of their contents were successfully achieved using the capillary column-gas chromatographic method. According to the obtained results, for rapeseed, sitosterol (1.54–2.36 g/kg) was the major component of total phytosterols, followed by campesterol (0.02–1.58 g/kg) and brassicasterol (0.26–0.58 g/kg). Regarding the olive varieties, the sitosterol content changed between 1.03 and 2.01 g/kg, followed by avenasterol ranging from 0.07 to 0.44 g/kg. The brassicasterol, campesterol and stigmasterol contents did not affect the total amount of sterols. The total phytosterol content ranged between 4.25 and 11.37 g/kg for rapeseed and 1.29 and 2.38 g/kg for olives.