A common feature of photosynthesis in practically all organisms is the assimilation of CO2 into organic matter via a catalyst called ribulose 1,5-bisphosphate carboxylase oxygenase (Rubisco) in the carbon assimilation cycle. One of the constraints on the process in terrestrial plants is conditions where CO2 becomes limiting because of high temperature, drought, or soil salinity. This can occur by restricting the entry of CO2 into leaves, by decreased stomatal conductance, by decreased cytoplasmic solubility of CO2, and by increased photorespiration (a process resulting from O2 competing with CO2 in Rubisco catalysis). In response to CO2 limitations, some terrestrial plants evolved mechanisms to concentrate CO2 around Rubisco through a C4 cycle that requires spatial separation of fixation of atmospheric CO2 into C4 acids, and the donation of CO2 from C4 acids via decarboxylases to Rubisco (called C4 plants). The paradigm for C4 photosynthesis in terrestrial plants for more than 35 years was that a dual-cell system, called Kranz leaf anatomy, is required for spatial separation of these functions. Surprisingly, recent research on species in family Chenopodiaceae has shown that C4 photosynthesis can occur within a single photosynthetic cell. Two very novel means of accomplishing this evolved in subfamily Suaedoideae. These systems function by spatial development of two cytoplasmic domains, which contain dimorphic chloroplasts. Emerging information on the biochemical and structural strategies for accomplishing C4 has promise for improving the productivity of rice, which lacks a CO2-concentrating mechanism, and for securing this important crop as a food supply under CO2-limited conditions predicted with global warming.