Polyimides are a group of high performance thermal stable dielectric materials used in diverse applications. In this article, we synthesized and developed a high-performance polyimide precursor ink for a Material Jetting (MJ) process. The proposed ink formulation was shown to form a uniform and dense polyimide film through reactive MJ utilising real-time thermo-imidisation process. The printed polyimide film showed a permittivity of 3.41 and degradation temperature around 500 °C, both of which are comparable to commercially available polyimide films. Benefiting from the capability of being able to selectively deposit material through MJ, we propose the use of such a formulation to produce complex circuit board structures by the co-printing of conductive silver tracks and polyimide dielectric layers. By means of selectively depositing 4 μm thick patches at the cross-over points of two circuit patterns, a traditional double-sided printed circuit board (PCB) can be printed on one side, providing the user with higher design freedom to achieve a more compact high performance PCB structure.