We introduce a new process that enables the ability to 3D-print high porosity materials and structures by combining the newly introduced 3D-Painting process with traditional salt-leaching. The synthesis and resulting properties of three 3D-printable inks comprised of varying volume ratios (25:75, 50:50, 70:30) of CuSO4 salt and polylactide-co-glycolide (PLGA), as well as their as-printed and salt-leached counterparts, are discussed. The resulting materials are comprised entirely of PLGA (F-PLGA), but exhibit porosities proportional to the original CuSO4 content. The three distinct F-PLGA materials exhibit average porosities of 66.6–94.4%, elastic moduli of 112.6-2.7 MPa, and absorbency of 195.7–742.2%. Studies with adult human mesenchymal stem cells (hMSCs) demonstrated that elevated porosity substantially promotes cell adhesion, viability, and proliferation. F-PLGA can also act as carriers for weak, naturally or synthetically-derived hydrogels. Finally, we show that this process can be extended to other materials including graphene, metals, and ceramics.