Utilizing photocatalytic CO2 reduction presents a promising avenue for combating climate change and curbing greenhouse gas emissions. However, maximizing its potential hinges on the development of materials that not only enhance efficiency but also ensure process stability. Here, we introduce Hiroshima University Silicate‐7 (HUS‐7) with immobilized Ti species as a standout contender. Our study demonstrates the remarkable photocatalytic activity of HUS‐7 in CO2 reduction, yielding substantially higher carbonaceous product yields compared to conventional titanium‐based catalysts TS‐1 and P25. Through thorough characterization, we elucidate that their boosted photocatalytic performance is attributed to the incorporation of isolated Ti species within the silica‐based precursor, serving as potent photoinduced active sites. Moreover, our findings underscore the crucial role of the Ligand‐to‐Metal Charge Transfer (LMCT) process in facilitating the photoactivation of CO2 molecules, shedding new light on key mechanisms underlying photocatalytic CO2 reduction.