We construct unramified central simple algebras representing 2-torsion classes in the Brauer group of a hyperelliptic curve, and show that every 2-torsion class can be constructed this way when the curve has a rational Weierstrass point or when the base field is C 1. In general, we show that a large (but in general proper) subgroup of the 2-torsion classes are given by the construction. Examples demonstrating applications to the arithmetic of hyperelliptic curves defined over number fields are given.