The purpose of this study is to examine the possible use of rice glycosphingolipids (RGSLs) as an emulsifier to form food grade microemulsions (mean particle size, 10–20 nm) and improve the absorption of CoQ10 with a poor solubility property by prepared emulsion. Because RGSLs could act as an auxiliary emulsifying agent, its addition to the surfactant/oil mixture decreased the emulsion’s particle size. This suggests that RGSLs exist between the water and oil phases to decrease oil droplet size via reduced interfacial tension. CoQ10-loaded microemulsion was also successfully prepared with RGSLs and powdered after freeze-drying with a cryoprotectant. CoQ10’s solubility in freeze-dried particles was dramatically improved compared to that of CoQ10 powder. Moreover, oral absorption of CoQ10 was significantly enhanced when administered via CoQ10-loaded microemulsion. The area under the plasma concentration–time curve for the microemulsion improved up to seven-fold compared to CoQ10 powder. The use of RGSLs could, therefore, be an effective processing technique for improving CoQ10’s solubility and absorption.