Arsenic (As) and fluoride (F⁻) are the two most conspicuous contaminants, in terms of distribution and menace, in aquifers around the world. While the majority of studies focus on the individual accounts of their hydro-geochemistry, the current work is an effort to bring together the past and contemporary works on As and F⁻ co-occurrence. Co-occurrence in the context of As and F⁻ is a broad umbrella term and necessarily does not imply a positive correlation between the two contaminants. In arid oxidized aquifers, healthy relationships between As and F⁻ is reported owing desorption based release from the positively charged (hydr)oxides of metals like iron (Fe) under alkaline pH. In many instances, multiple pathways of release led to little or no correlation between the two, yet there were high concentrations of both at the same time. The key influencer of the strength of the co-occurrence is seasonality, environment, and climatic conditions. Besides, the existing primary ion and dissolved organic matter also affect the release and enrichment of As–F^- in the aquifer system. Anthropogenic forcing in the form of mining, irrigation return flow, extraction, recharge, and agrochemicals remains the most significant contributing factor in the co-occurrence. The epidemiological indicate that the interface of these two interacting elements concerning public health is considerably complicated and can be affected by some uncertain factors. The existing explanations of interactions between As–F are indecisive, especially their antagonistic interactions that need further investigation. “Multi-contamination perspectives of groundwater” is an essential consideration for the overarching question of freshwater sustainability.