The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science1. Whether based on inorganic2, 3, 4, 5 or organic6, 7, 8 materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. ‘Printed electronics’ is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials9, 10, 11. However, because of the strong self-organizing tendency of the deposited materials12, 13, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization14 with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctylbenzothieno[3,2-b]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4cm2V−1s−1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.