The use of electrospinning technology to construct edible nano-delivery carriers has been one of the most important way to improve the utilize efficiency of novel localized drugs or food active components. However, it is still challenging to develop nanofibers with natural polymers due to many problems such as the toxicity of organic reagent and difficulty in forming the nanostructure. In this study, natural plant polysaccharide guar gum （guar gum，GG） were selected as the fiber forming substrate to co-load corn starch（starch，ST）, and successfully developed a edible GG/ST composite nanofiber delivery carrier. The results showed that the minimum molecular entanglement concentration of GG as a fiber forming matrix was 1.1 wt%. A series of GG/ST composite solution were prepared (4∶1, 2∶1, 1∶1, and 1∶4). Through static and dynamic rheological testing of GG/ST solution and characterization of fiber microstructure, it was found that the ratio of GG/ST at 2∶1 was the optimal concentration to obtain the uniform and smooth fiber nanostructure. When the ST content is 5w%~10w%, beaded fiber morphology in the structure and unnormal distribution of diameter was observed, and electrospinning process had little effect on the improvement of the fiber structure. This study provide a support for developing edible nano carriers and offered a basis for developing targeted drugs or functional foods in the future.