We exhibit a sharp Castelnuovo bound for the i-th plurigenus of a smooth variety of given dimension n and degree d in the projective space P r , and classify the varieties attaining the bound, when n2, r2n+1, d>>r and i>>r. When n=2 and r=5, or n=3 and r=7, we give a complete classification, i.e. for any i1. In certain cases, the varieties with maximal plurigenus are not Castelnuovo varieties, i.e. varieties with maximal geometric genus. For example, a Castelnuovo variety complete intersection on a variety of dimension n+1 and minimal degree in P r , with r>(n 2 +3n)/(n–1), has not maximal i-th plurigenus, for i>>r. As a consequence of the bound on the plurigenera, we obtain an upper bound for the self-intersection of the canonical bundle of a smooth projective variety, whose canonical bundle is big and nef.