Luminescent solar concentrators (LSCs) are luminescent waveguide layers that convert sunlight into specific wavelengths which are then guided by total internal reflection to a PV device located at the edges of the LSC. Their ability to concentrate sunlight onto small areas makes LSCs a useful complement to silicon-based PVs in a series of applications, such as urban integration and flexible fabrics towards mobile solar-energy. Challenges for the luminescent layer include the use of low-cost and sustainable nature-based organic molecules. We report novel chlorophyll-based LSCs with emission properties in the red/NIR spectral region. Here, chlorophyll molecules extracted from Spirulina maxima, an abundant cyanobacterium and an attractive natural source, are immobilized in organic–inorganic di- and tri-ureasil matrices enabling the production of sustainable LSCs. At low chlorophyll concentrations (<3 × 10¹⁷ molecules per cm³), the photophysical properties of the chlorophyll molecules after incorporation into the hybrids closely resemble those in ethanolic solution (with an absolute emission quantum yield of ∼0.16 and a fluorescence lifetime of ∼8 ns). The LSCs were coupled to a Si-based commercial PV device revealing optical conversion efficiency and power conversion efficiency values of ∼3.70% and 0.10%, respectively, illustrating the potential of this approach for the development of nature-based LSCs meeting the requirements of reliable, sustainable and competitive energy systems.