Ink additives based on oppositely charged bPEs were synthesized from poly(ethylene glycol) in a two-step process. In the first step, methoxy poly(ethylene glycol)113-poly(allyl glycidyl ether)45 (mPEO113-PAGE45) AB diblock copolymers or poly(ally glycidyl ether)30-poly(ethylene glycol)455poly(ally glycidyl ether)30 (PAGE30-PEO455-PAGE30) ABA triblock copolymers were synthesized by ring-opening anionic polymerization. In the second step, the PAGE blocks were functionalized with ionic (guanidinium or sulfonate) moieties using thiol-ene click chemistry to yield diblock or triblock polyelectrolytes (DbPE or TbPE, respectively) (Figure ). Mixing equimolar aqueous solutions of cationic and anionic bPEs resulted in swift electrostatic self-assembly of polyelectrolyte complex (PEC) hydrogels with characteristic PEC microstructures. DbPEs assembled into micelles with the charged A blocks forming the micelle core and the neutral B blocks forming the corona, while TbPEs formed interconnected networks, wherein the neutral B midblocks bridged the PEC domains comprising the charged A endblocks (Figure ) .