The ecological success of purple sulfur bacteria (PSB) is linked to their ability to collect near‐infrared solar energy by membrane‐integrated, pigment–protein photocomplexes. These include a Core complex containing both light‐harvesting 1 (LH1) and reaction centre (RC) components (called the LH1–RC photocomplex) present in all PSB and a peripheral light‐harvesting complex present in most but not all PSB. In research to explain the unusual absorption properties of the thermophilic purple sulfur bacterium Thermochromatium tepidum, Ca2+ was discovered bound to LH1 polypeptides in its LH1–RC; further work showed that calcium controls both the thermostability and unusual spectrum of the Core complex. Since then, Ca2+ has been found in the LH1–RC photocomplexes of several other PSB, including mesophilic species, but not in the LH1–RC of purple non‐sulfur bacteria. Here we focus on four species of PSB—two thermophilic and two mesophilic—and describe how Ca2+ is integrated into and affects their photosynthetic machinery and why this previously overlooked divalent metal is a key nutrient for their ecological success.