Silk Fibroin (SF) is a natural polymer obtained from the Bombyx mori silkworm. It has been used in bone tissue engineering thanks to its favorable biocompatibility, adhesion, low biodegradability, and tensile strength properties. Electrospinning is a technique to develop nanofibers. It uses high voltages to convert polymer solutions into porous nanostructured scaffolds with a good ratio between superficial area and volume. In this paper, we examine the effect of the electrospinning parameters on fiber morphology once the spun fibers have been treated. In addition, we present different physicochemical characterizations of electrospun SF scaffolds such as their morphology (via Scanning Electron Microscopic—SEM—), crystalline structure (via Fourier Transform Infrared—FTIR—spectroscopy and X-Ray Diffraction—XRD—), thermal characteristics (via Differential Scanning Calorimetry—DSC—and Thermogravimetric Analysis—TGA—), and mechanical properties (tensile strength). Finally, we discuss the potential applications and impacts of electrospun SF in bone tissue engineering and future research trends.