Incorporation of polymer chain entanglements within a single network can synergistically improve stiffness and toughness, yet attaining such dense entanglements through vat photopolymerization additive manufacturing [e.g., digital light processing (DLP)] remains elusive. We report a facile strategy that combines light and dark polymerization to allow constituent polymer chains to densely entangle as they form within printed structures. This generalizable approach reaches high monomer conversion at room temperature without the need for additional stimuli, such as light or heat after printing, and enables additive manufacturing of highly entangled hydrogels and elastomers that exhibit fourfold- to sevenfold-higher extension energies in comparison to that of traditional DLP. We used this method to print high-resolution and multimaterial structures with features such as spatially programmed adhesion to wet tissues.