Fabrication and functionalization of hydrogels from well-defined dendron-polymer-dendron conjugates is accomplished using sequential radical thiol-ene "click" reactions. The dendron-polymer conjugates were synthesized using an azide-alkyne "click" reaction of alkene-containing polyester dendrons bearing an alkyne group at their focal point with linear poly(ethylene glycol)-bisazides. Thiol-ene "click" reaction was used for crosslinking these alkene functionalized dendron-polymer conjugates using a tetrathiol-based crosslinker to provide clear and transparent hydrogels. Hydrogels with residual alkene groups at crosslinking sites were obtained by tuning the alkene-thiol stoichiometry. The residual alkene groups allow efficient postfunctionalization of these hydrogel matrices with thiol-containing molecules via a subsequent radical thiol-ene reaction. The photochemical nature of radical thiol-ene reaction was exploited to fabricate micropatterned hydrogels. Tunability of functionalization of these hydrogels, by varying dendron generation and polymer chain length was demonstrated by conjugation of a thiol-containing fluorescent dye. (C) 2015 Wiley Periodicals, Inc.