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Biological soil crusts (BSC) encompassing green algae, cyanobacteria, lichens, bryophytes, heterotrophic bacteria and microfungi are keystone species in arid environments because of their role in nitrogen- and carbon-fixation, weathering and soil stabilization, all depending on the photosynthesis of the BSC. Despite their importance, little is known about the BSCs of the Atacama Desert, although especially crustose chlorolichens account for a large proportion of biomass in the arid coastal zone, where photosynthesis is mainly limited due to low water availability. Here, we present the first hyperspectral reflectance data for the most wide-spread BSC species of the southern Atacama Desert. Combining laboratory and field measurements, we establish transfer functions that allow us to estimate net photosynthesis rates for the most common BSC species. We found that spectral differences among species are high, and differences between the background soil and the BSC at inactive stages are low. Additionally, we found that the water absorption feature at 1420 nm is a more robust indicator for photosynthetic activity than the chlorophyll absorption bands. Therefore, we conclude that common vegetation indices must be taken with care to analyze the photosynthesis of BSC with multispectral data.