The context of a photogeochemical reaction is implicitly the surface of Earth, since that is where sunlight is available (although other sources of light such as chemiluminescence would not be strictly excluded from photogeochemical study). Reactions may occur among components of land such as rocks, soil and detritus; components of surface water such as sediment and dissolved organic matter; and components of the atmospheric boundary layer directly influenced by contact with land or water, such as mineral aerosols and gases. Visible and medium- to long-wave ultraviolet radiation is the main source of energy for photogeochemical reactions; wavelengths of light shorter than about 290 nm are completely absorbed by the present atmosphere, and are therefore practically irrelevant, except in consideration of atmospheres different from that of Earth today.
Photogeochemical reactions are limited to chemical reactions not facilitated by living organisms. The reactions comprising photosynthesis in plants and other organisms, for example, are not considered photogeochemistry, since the physiochemical context for these reactions is installed by the organism, and must be maintained in order for these reactions to continue (i.e. the reactions cease if the organism dies). In contrast, if a certain compound is produced by an organism, and the organism dies but the compound remains, this compound may still participate independently in a photogeochemical reaction even though its origin is biological (e.g. biogenic mineral precipitates or organic compounds released from plants into water).
The study of photogeochemistry is primarily concerned with naturally occurring materials, but may extend to include other materials, inasmuch as they are representative of, or bear some relation to, those found on Earth. For example, many inorganic compounds have been synthesized in the laboratory to study photocatalytic reactions. Although these studies are usually not undertaken in the context of environmental or Earth sciences, the study of such reactions is relevant to photogeochemistry if there is a geochemical implication (i.e. similar reactants or reaction mechanisms occur naturally). Similarly, photogeochemistry may also include photochemical reactions of naturally occurring materials that are not touched by sunlight, if there is the possibility that these materials may become exposed (e.g. deep soil layers uncovered by mining).
Except for several isolated instances, studies that fit the definition of photogeochemistry have not been explicitly specified as such, but have been traditionally categorized as photochemistry, especially at the time when photochemistry was an emerging field or new facets of photochemistry were being explored. Photogeochemical research, however, may be set apart in light of its specific context and implications, thereby bringing more exposure to this "poorly explored area of experimental geochemistry". Past studies that fit the definition of photogeochemistry may be designated retroactively as such.