Electrospinning utilizes electrostatic forces to produce ultrafine fibers from polymer solutions or melts. A standard electrospinning setup comprises a high-voltage power supply, spinneret, and collector. The process involves the formation of a Taylor cone, jet initiation, and eventual fiber deposition and solidification on the collector. Charge generation, transport, and residual charge significantly influence fiber morphology and properties. Charge generation mechanisms like field emission and field-enhanced ion dissociation, as well as charge transfer from solvent to air during evaporation, are crucial. The electrospinning jet dynamics, including straight jet analysis, jet thinning mechanisms, scaling laws governing fiber diameter, and hydrodynamic instabilities (axisymmetric, whipping, buckling), determine fiber morphology. Polymer dissolution, disentanglement, and solvent evaporation effects on molecular orientation and properties are key to nanofiber formation. This chapter overviews these fundamental aspects underlying electrospinning processes.