The creation of biomaterials with aligned fibers offers broad applications in tissue regeneration, guiding cell organization and physiological cues, and providing appropriate mechanical properties for many biomedical applications. Herein, for the first time, highly aligned electrospun membranes are designed and developed using glycopolymers. The membranes retain the strong mechanical properties of polycaprolactone, and fiber alignment facilitates the creation of anisotropic mechanical properties, enabling failure stress to be manipulated by an order of magnitude relative to randomly ordered fibers. Biocompatibility and cell attachment in these materials are characterized using tenocytes as a cell model. Both random and aligned fiber glycopolymers show promising biocompatibility, but aligned glycopolymer fibers additionally offer patterning to guide cell organization. These materials potentially provide a novel platform for tissue regeneration studies, demonstrating that the sugar-lectin interaction can produce materials capable of managing cell guidance.