The need for high-precision microprinting processes that are controllable, scalable, and compatible with different materials persists throughout a range of biomedical fields. Electrospinning techniques offer scalability and compatibility with a wide arsenal of polymers, but typically lack precise three-dimensional (3D) control. We found that charge reversal during 3D jet writing can enable the high-throughput production of precisely engineered 3D structures. The trajectory of the jet is governed by a balance of destabilizing charge-charge repulsion and restorative viscoelastic forces. The reversal of the voltage polarity lowers the net surface potential carried by the jet and thus dampens the occurrence of bending instabilities typically observed during conventional electrospinning. In the absence of bending instabilities, precise deposition of polymer fibers becomes attainable. The same principles can be applied to 3D jet writing using an array of needles resulting in complex composite materials that undergo reversible shape transitions due to their unprecedented structural control.