We give a proof of Mukai’s theorem on the existence of certain exceptional vector bundles on prime Fano threefolds. To our knowledge this is the first complete proof in the literature. The result is essential for Mukai’s biregular classification of prime Fano threefolds, and for the existence of semiorthogonal decompositions in their derived categories. Our approach is based on Lazarsfeld’s construction that produces vector bundles on a variety from globally generated line bundles on a divisor, on Mukai’s theory of stable vector bundles on K3 surfaces, and on Brill–Noether properties of curves and (sensu Mukai) of K3 surfaces.