Recent investigations of anchialine caves and sinkholes have identified complex food webs dependent on detrital and, in some cases, chemosynthetically produced organic matter. Chemosynthetic microbes in anchialine systems obtain energy from reduced compounds produced during organic matter degradation (e.g., sulfide, ammonium, and methane), similar to what occurs in deep ocean cold seeps and mud volcanoes, but distinct from dominant processes operating at hydrothermal vents and sulfurous mineral caves where the primary energy source is mantle derived. This review includes case studies from both anchialine and non-anchialine habitats, where evidence for in situ chemosynthetic production of organic matter and its subsequent transfer to higher trophic level metazoans is documented. The energy sources and pathways identified are synthesized to develop conceptual models for elemental cycles and energy cascades that occur within oligotrophic and eutrophic anchialine caves. Strategies and techniques for testing the hypothesis of chemosynthesis as an active process in anchialine caves are also suggested.