This review presents a holistic overview of the occurrence, mobilization, and pathways of arsenic (As) from predominantly geogenic sources into different near-surface environmental compartments, together with the respective reported or potential impacts on human health in Latin America. The main sources and pathways of As pollution in this region include: (i) volcanism and geothermalism: (a) volcanic rocks, fluids (e.g., gases) and ash, including large-scale transport of the latter through different mechanisms, (b) geothermal fluids and their exploitation; (ii) natural lixiviation and accelerated mobilization from (mostly sulfidic) metal ore deposits by mining and related activities; (iii) coal deposits and their exploitation; (iv) hydrocarbon reservoirs and co-produced water during exploitation; (v) solute and sediment transport through rivers to the sea; (vi) atmospheric As (dust and aerosol); and (vii) As exposure through geophagy and involuntary ingestion. The two most important and well-recognized sources and mechanisms for As release into the Latin American population's environments are: (i) volcanism and geothermalism, and (ii) strongly accelerated As release from geogenic sources by mining and related activities. Several new analyses from As-endemic areas of Latin America emphasize that As-related mortality and morbidity continue to rise even after decadal efforts towards lowering As exposure. Several public health regulatory institutions have classified As and its compounds as carcinogenic chemicals, as As uptake can affect several organ systems, viz. dermal, gastrointestinal, peptic, neurological, respiratory, reproductive, following exposure. Accordingly, ingesting large amounts of As can damage the stomach, kidneys, liver, heart, and nervous system; and, in severe cases, may cause death. Moreover, breathing air with high As levels can cause lung damage, shortness of breath, chest pain, and cough. Further, As compounds, being corrosive, can also cause skin lesions or damage eyes, and long-term exposure to As can lead to cancer development in several organs.