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Polysucrose (PSuc) is hydrophilic, has excellent biocompatibility with cells as a density gradient and is resistant to enzymes. Its use in electrospun mats for tissue engineering applications has not been investigated due to its amorphous nature. For spinnability and robustness, polysucrose was blended with poly-L-lactide (PLLA) and polydioxanone (PDX) respectively and electrospun into nanofibrous mats. Interaction with cells was assessed using L929 mouse fibroblasts and HaCaT keratinocytes separately and in co-culture. Effect of parameters such as porosity, fiber diameter, surface wettability and mechanical properties of mats on cell-scaffold interactions was studied. Depending on nature and composition of mats, fibroblasts showed dendritic, spindle or round cell morphologies along with the formation of lamellipodia, filopodia, fibrillar or fiber-like projections of 100 nm and 200-300 nm in diameter respectively from the periphery or center of cells. Granular extracellular matrix was formed on both PLLA-PSuc and PDX-PSuc 50-50 seeded with keratinocytes. Growth of keratinocytes was enhanced in co-culture with fibroblasts with the formation of a skin-like layer. Both cells showed the ability to form multilayer structures. The mats maintained their physical integrity during the period of study. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 3275-3291, 2018.