β-Sitosterol (Sit) and stearic acid (SA) were combined at varying ratios (w/w) and added to sunflower oil (SFO) at the concentration of 20 g/100 g oil for preparing edible fat-like oleogel. The oleogel was characterized using an optical microscope, Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD), differential scanning calorimeter, and texture analyzer. The oil-binding capacity, melting temperature, and firmness of the oleogel increased with the increase in the amount of SA in the gelator combination (Sit:SA, w/w). The microscopic analysis showed that the gel network formed based on the crystallization and self-organization of gelator molecules, and both gelators showed an independent crystalline behavior in the oleogel. In addition, the FTIR spectra showed that the gel network formed via physical entanglements and was stabilized by non-covalent interactions such as hydrogen bonding. Furthermore, XRD diffraction patterns indicated high lateral packing of molecular layers in oleogel prepared with the Sit and SA combination compared with oleogel prepared with a single gelator. On the other hand, for studying the effect of varying concentrations of gelator combinations, the Sit3:SA2 (w/w) combination was added to SFO at concentrations of 10, 15, 20, 25, and 30 g/100 g oil. Specific characteristics such as the oil-binding capacity and firmness of the oleogel improved as the concentration of the gelator combination (Sit3:SA2) increased from 10 up to 30 g/100 g oil. Therefore, it can be concluded that the saturated fat alternative oleogel can be prepared from SFO with a specific Sit and SA combination ratio and concentration.