Polymerization in volume/bulk is one of the most important processes used in science and in industry to form solid polymers used in multiple different applications. The migration and transport of molecular polymerization initiators are problematic for commercially used photo‐polymerization procedures. ZnO not only is a well‐known photo‐semiconductor but has the potential to be used as an enlarged size photo‐initiation system. A high reactivity modification, firstly systematically investigated using novel light‐emitting diode illumination and two benchmarked resins is presented here. The curing potential of layers up to 1.4 mm is proven and first indications of differences in oxygen dependencies of such initiating systems are discovered. Additionally, the optimized synthesis procedure (0.45 mol L−1 Zn2+ at room temperature) is presented which allows to perform systematic variation of the ZnO surface. Starting from one approach/batch, the content of the modification is systematically increased.