A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Río Tinto, Río Odiel, and Río Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66 µM at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3 nmol L^− 1s^− 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3 nmol L^− 1s^− 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Río Tinto in about 30 days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research.