Solution-based, direct-write patterning by an automated, computer-controlled, inkjet technique is of particular interest in a wide variety of industrial fields. We report the construction of three-dimensional (3D), micropatterned structures by polymer inkjet printing. A piezoelectric, drop-on-demand (DOD) inkjet printing system and a common polymer, PVA (poly(vinyl alcohol)), were explored for 3D construction. After a systematic preliminary study with different solvent systems, a mixture of water and DMSO was chosen as an appropriate solvent for PVA inks. The use of water as a single solvent resulted in frequent PVA clogging when the nozzles were undisturbed. Among the tested polymer ink compositions, the PVA inks in a water/DMSO mixture (4/1 v/v) with concentrations of 3 to 5 g/dL proved to be appropriate for piezoelectric DOD inkjet printing because they were well within the proper viscosity and surface tension range. When a dot was printed, the so-called ‘coffee-ring effect’ was significant, but its appearance was not prominent in line printing. The optimal polymer inkjet printing process was repeated slice after slice up to 200 times, which produced a well-defined, 3D micro-patterned surface. The overall results implied that piezoelectric DOD polymer inkjet printing could be a powerful, solid-freeform, fabrication technology to create a controlled 3D architecture.