In this work, we show that the periplasm, an underappreciated subcellular region in materials research, can offer a nongenetic pathway for biomineralization of metastable semiconductor nanoclusters. Under light stimulation, the metastable semiconductor nanoclusters could couple with the electron transport chain to increase ATP levels and enhance malate production in the living hybrids. Using the E. coli strain as a model, the current system to develop periplasmic biointerface for enhanced solar-to-chemical production might be extended to other bacterial cells to potentially endow additional sustainability level to the bioremediation applications