The largest veins in your arm are the brachial veins, located alongside the brachial artery.
These deep veins are actually a pair of veins (venae comitantes) that run on either side of the brachial artery, the major blood vessel of the upper arm. They play a critical role in returning blood from the lower arm and hand back to the heart. While not visible from the surface, their size and importance make them the "biggest" in terms of functional significance.
Think of them as the major "highway" for blood returning from your forearm and hand. Smaller veins converge into larger ones, eventually leading to the brachial veins, which then flow into the axillary vein (located in the armpit) and ultimately contribute to the venous system that returns blood to the heart.
Therefore, when considering the largest vein, it's the brachial veins, situated alongside the brachial artery in your upper arm.