Cyclodextrins (CDs) are cyclic oligosaccharides derived from the enzymatic degradation of starch. Emulsifying functionality of β-cyclodextrin (β-CD) upon its complexation with selected solvents (octanol, decane, and toluene) was studied. In several tests, the three-phase systems containing the emulsion fraction in the middle position were obtained. The examination of variations in the phase behavior of the test systems showed that the decane/β-CD/water system had the highest emulsion phase volume when β-CD at concentration of 10% w/v was used. A reduction in interfacial tension (IFT) of the oil–water interface in each test system was observed with the following order: toluene, decane, and octanol. The precipitated fraction obtained upon centrifugation of the emulsion phase, was structurally characterized as the inclusion complex (IC) formed between β-CD and each of the three test solvents. The wettability of the IC particles was determined through contact angle measurement and formation of the oil-in-water (O/W) Pickering emulsions was confirmed (θow<90°). With use of size distribution data, the ICs particles as the microparticles (1–10 µm) were found to be the main species involved in the formation and stabilization of the emulsions.