Food polysaccharides are well acclaimed in the field of delivery systems due to their natural safety, biocompatibility with the human body, and capability of incorporating/releasing various bioactive compounds. Electrospinning, a straightforward atomization technique that has been attracting researchers worldwide, is also versatile for coupling food polysaccharides and bioactive compounds. In this review, several popular food polysaccharides including starch, cyclodextrin, chitosan, alginate, and hyaluronic acid are selected to discuss their basic characteristics, electrospinning conditions, bioactive compound release characteristics, and more. Data revealed that the selected polysaccharides are capable of releasing bioactive compounds from as rapidly as 5 s to as prolonged as 15 days. In addition, a series of frequently studied physical/chemical/biomedical applications utilizing electrospun food polysaccharides with bioactive compounds are also selected and discussed. These promising applications include but are not limited to active packaging with 4-log reduction againstE. coli,L. innocua,andS. aureus; removal of 95% of particulate matter (PM) 2.5 and volatile organic compounds (VOCs); heavy metal ion removal; increasing enzyme heat/pH stability; wound healing acceleration and enhanced blood coagulation, etc. The broad potentials of electrospun food polysaccharides loaded with bioactive compounds are demonstrated in this review.