AbstractHigh‐molecular biodegradable and bioresorbable polymers are widely used in tissue engineering applications. In this work, a high‐resolution 3D printing technique, thermally assisted electrohydrodynamic jet (TAEJ) printing, is developed for patterning high‐molecular weight biopolymer 3D structures. Boiling point graded polyvinylpyrrolidone (PVP) and PVP/polycaprolactone biopolymer inks are prepared. The resultant effects of electrohydrodynamic force and thermal field are applied on these polymer ink, to form a stable and controllable sub‐micrometer scale jet at the needle tip. Fine jet 2D period patterns and 3D high aspect ratio structures of the biopolymer inks are directly printed using fine jet at a typical feature size of sub‐micrometer. Furthermore, TAEJ printing of 3D heterogeneous high‐molecular weight biopolymer scaffold is demonstrated. Cell culture shows high biocompatibility and cartilage regeneration in vitro, which provides a great potential for tissue engineering applications.