Inspired by photosynthesis in nature, artificial photosynthesis (AP) systems have been widely investigated in the context of energy and environmental research. Here we report a noble-metal-free AP system for visible-light-driven H2 generation from aqueous solutions consisting of fluorescein (FL) as photosensitizer, single-layer ultrasmall MoS2 nanoplates embedded in carbon nanofibers (CNF) as electron relay and redox catalyst, and triethanolamine (TEOA) as sacrificial electron donor. This CNF–MoS2/FL system exhibits outstanding H2 evolution performance, with an H2 generation rate that exceeds not only both MoS2/FL (by 100%) and CNF/FL (by 1100%), but also the Pt/FL system (by 40%). The excellent photocatalytic activity of this CNF–MoS2/FL system can be ascribed to the synergistic effects of CNF and MoS2 coupling: (1) the simultaneous presence of MoS2 with its delocalized and increased Mo 4d unoccupied states and of CNF with increased graphitic characteristics enables electron transfer from FL∗ to MoS2 via CNF electron relay; (2) the single-layered ultrasmall MoS2 nanoplates with short effective lengths for electron transfer and high density of reactive S-edges effectively catalyze the H2 evolution reaction (HER). The presented work successfully fabricated a highly efficient AP system for solar H2 production from a fully aqueous solution and indicated CNF–MoS2 as a promising candidate to replace Pt for solar fuel conversion.