Heavy metals are toxic substances released into the environment, contributing to a variety of toxic effects on living organisms in food chain by accumulation and biomagnifications. Certain pollutants such as arsenic (As) remain in the environment for an extensive period. They eventually accumulate to levels that could harm physiochemical properties of soils and lead to loss of soil fertility and crop yield. Arsenic, when not detoxified, may trigger a sequence of reactions leading to growth inhibition, disruption of photosynthetic and respiratory systems, and stimulation of secondary metabolism. Plants respond to As toxicity by a variety of mechanisms including hyperaccumulation, antioxidant defense system, and phytochelation. Arbuscular mycorrhizae symbiosis occurs in almost all habitats and climates, including disturbed soils. There is growing evidence that arbuscular mycorrhizae fungi may alleviate metal/metalloid toxicity to host plant. Here, we review (1) arsenic speciation in the environment and how As is taken up by the roots and metabolised within plants, and (2) the role of arbuscular mycorrhizae in alleviating arsenic toxicity in crop plants.