Electrospinning technology underwent rapid development in recent years, which can be used for fabricating electrospun fibers with different morphologies and multidimensional structures. These fibers are widely applied in medical diagnosis, tissue engineering, replica molding and other applications. Here we review the recent advances in the electrospinning technology, especially technical progress in fabricating electrospun fibers and assemblies with multidimensional structures, and the biomedical applications of these fibers.