Electrospraying (ES) is a potential-driven process of liquid atomization, which is employed in the field of analytical chemistry, particularly as an ionization technique for mass spectrometric analyses of biomolecules. In this review, we demonstrate the extraordinary versatility of the electrospray by overviewing the specifics and advanced applications of ES-based processing of low molecular mass compounds, biomolecules, polymers, nanoparticles, and cells. Thus, under suitable experimental conditions, ES can be used as a powerful tool for highly controlled deposition of homogeneous films or various patterns, which may sometimes even be organized into 3D structures. We also emphasize its capacity to produce composite materials including encapsulation systems and polymeric fibers. Further, we present several other, less common ES-based applications. This review provides an insight into the remarkable potential of ES, which can be very useful in the designing of innovative and unique strategies.