Photocurable colloid binders are provided that overcome deficiencies associated with 3D printing of high molecular weight polymers via VAT photopolymerization. Methods of additive manufacturing are also provided using the binders. The approaches described herein effectively decouple the viscosity-molecular weight relationship by synthesizing and processing photo-reactive aqueous colloids that are sequestered within a photocrosslinkable scaffold. Sequestering polymers within discrete internal phases prevents inter-particle entanglement of the polymer chains, thus ensuring low viscosity. VP of polymer colloids results in a solid green body embedded with high molecular weight polymer particles. A post-processing heated drying step allows the polymers to coalesce and further entangle, forming a semi-interpenetrating network with mechanical performance of the high molecular weight material. The resins can further include inorganic particles such as silica and other ceramics, metal particles, and the like. The coalescence can result in the particles being encapsulated in polymer, yielding unique hybrid materials with tunable properties.