Electrospinning is a versatile and fascinating technology to produce ultra-fine fibers with diameter from several micrometers to a few nanometers. So far, huge number of materials such as polymers, composite ceramics, metals, carbon nanotubes, even bacteria and virus can be fabricated/incorporated into micro- and nano-fibers by directly electrospinning or through post-spinning process. Many publications including reviews and research papers were focused on the process, properties, and applications of electrospinning or electrospun nanofibers (Afifi et al. 2010, Agarwal et al. 2013, Agarwal et al. 2008, Greiner and Wendorff 2007, Huang et al. 2003, Kanani and Bahrami 2010, Li and Xia 2004, Sill and von Recum 2008, Wu et al. 2013, Zucchelli et al. 2011). The electrospun nanofibers and nanofibrous materials have unique properties, such as ultra-fine diameter, huge surface area to volume ratio (about a thousand times higher than that of human hair), large porosity, high aspect ratio of length to diameter, excellent mechanical properties due to the high molecular orientation along fiber axis, and easy-tailed nanofiber products. However, for the practical applications, electrospun nanofibers with proper mechanical properties are highly required. In this chapter, several approaches to achieve improved mechanical properties of electrospun fibers will be presented.