In the field of biomaterials starch‐based polymers have been widely studied for several different applications, including scaffolds for tissue engineering. Recently, electrospinning has been gaining interest as a promising method to manufacture highly porous 3D structures. Such structures provide a high surface area for cell attachment and proliferation, being adequate for several uses in tissue engineering. The aim of the current work is to develop nanofiber‐based constructs from starch‐polycaprolactone (SPCL 30/70 wt%) blends by means of electrospinning and to study the effect of different solvents. Solutions of 5–15 wt% either in acetic acid or chloroform were electrospun to aluminum foil. The voltage used was 30 kV and the counter‐electrode distance was 25 cm. The microstructure of the obtained constructs was characterized by using scanning electron microscopy (SEM). It was possible to obtain highly porous 3D scaffolds with a typical nanofiber‐mesh structure by using electrospinning from different SPCL‐solvent solutions. Electrospinning was most successful when using higher concentrations (15 wt%). With lower concentrations the process was not very feasible and at a concentration of 5 wt% it was not possible to obtain fibers. The diameter of the fibers obtained was 130–180 nm. SEM analysis revealed the presence of particles which are assumed to be starch. The particles were interconnected by the nanofibers. It is possible to produce highly porous nanofiber‐based constructs from SPCL by using electrospinning. Such constructs may have applications in tissue engineering of different tissues, such as bone, skin and cartilage.

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