Aqueous self-assembly of the oppositely charged pairs of DbPEs or TbPEs was harnessed to create a hydrogel scaffolding for the low-viscosity, non-extrudable solutions of crosslinkable precursors, thus providing structural stability and interim protection against uncontrolled dilution. Previously, we have shown that inclusion of photocurable precursor polymers does not impede with the PEC self-assembly . In this work, GelMA was used as a representative photocrosslinkable precursor. While GelMA solutions exhibit excellent printing performance near the gelling point (~ 22 °C) and has therefore become a widely used ink for 3D bioprinting , its water-like viscosity at 37 °C is similar to most synthetic precursors which suffer from poor printability. Mixing the GelMA precursor with the oppositely charged DbPEs resulted in extrudable GelMA/DbPE hydrogels comprising GelMA chains interspersed among jammed PEC micelles. Subsequent photocrosslinking of the GelMA precursors was induced by ultraviolet/visible light irradiation and led to the formation of hybrid GelMA/DbPE hydrogels (Figure ). Similarly, mixing of GelMA with the oppositely charged TbPEs resulted in homogenous and extrudable GelMA/TbPE hydrogels comprising an interconnected PEC network with dispersed GelMA chains. After photocrosslinking, hybrid GelMA/TbPE hydrogels with interpenetrating covalent and non-covalent networks were formed (Figure ). After photocrosslinking, covalently and electrostatically double-crosslinked hydrogels were formed.