The electrohydrodynamic (EHD) direct-writing technique can be used to print solid/liquid straight/serpentine nanofibers onto a large-area substrate, in a direct, continuous, and controllable manner. It is a high-efficiency and cost-effective solution-processable technique to satisfy increasing demands of large-area micro/nano-manufacturing. It is ground-breaking to direct-write sub-100 nm fibers on a rigid/flexible substrate using organic materials. A comprehensive review is presented on the research and developments related to the EHD direct-writing technique and print heads. Many developments have been presented to improve the controllability of the electrospun fibers to form high-resolution patterns and devices. EHD direct-writing is characterized by its non-contact, additive and reproducible processing, high resolution, and compatibility with organic materials. It combines dip-pen, inkjet, and electrospinning by providing the feasibility of controllable electrospinning for sub-100 nm nanofabrication, and overcomes the drawbacks of conventional electron-beam lithography, which is relatively slow, complicated and expensive.