The gelation of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has gained popularity for its potential applications in three dimensions, while possessing tissue-like mechanical properties, high conductivity, and biocompatibility. However, the fabrication of arbitrary structures, especially via inkjet printing, is challenging because of the inherent gel formation. Here, microreactive inkjet printing (MRIJP) is utilized to pattern various 2D and 3D structures of PEDOT:PSS/IL hydrogel by in-air coalescence of PEDOT:PSS and ionic liquid (IL). By controlling the in-air position and Marangoni-driven encapsulation, single droplets of the PEDOT:PSS/IL hydrogel as small as a diameter of ≈260 μm are fabricated within ≈600 μs. Notably, this MRIJP-based PEDOT:PSS/IL has potential for freeform patterning while maintaining identical performance to those fabricated by the conventional spin-coating method. Through controlled deposition achieved via MRIJP, PEDOT:PSS/IL can be transformed into different 3D structures without the need for molding, potentially leading to substantial progress in next-generation bioelectronics devices.