The resolution of inkjet printing technology is determined by wetting and evaporation processes after the jet drop contacts the substrate. Here, the wetting of different picoliter solubilized polymer droplets jetting onto one-end-closed porous alumina was investigated. The selected polymers are commonly used in inkjet ink. The synergistic effects of the hierarchical structure and substrate surface modification were used to control the behavior of polymer-based ink drops. A model that invokes the effect of surface tension was applied to calculate the amount of polymer solution penetrating into the pores. The calculation corroborates experimental observations and shows that the volume of polymer solution in the pores increases with an increase in pore radius and depth, resulting in less solution remaining on the substrate surface. The structure of the porous substrate coupled with intrinsic polymer properties and surface modifications all contribute to the resolution that can be achieved via inkjet printing.