Electrospinning at relatively low polymer concentrations produces polymer particles rather than fibers. To study the relationship between solvent characteristics and particle morphologies, PMMA was electrospun from seven different solvents and PSVPh random copolymers were electrospun from solutions in MEK. High-speed photography was used to visualize the particle-formation process. Based on these studies, a qualitative relationship between the solvent properties and the electrospun particle morphologies is discussed. By tailoring the solution properties and electrospinning conditions, particles with different morphologies (porous polygonal particles, solid polygonal particles, hollow spheres, cups etc) can be produced.