Superheating of Bi(0001) by about 90 K above the bulk melting temperature is observed using time-resolved reflection high-energy electron diffraction with ∼200-ps time resolution. Larger temperature excursions above the bulk melting temperature result in melting accompanied by irreversible laser damage to the surface. The rhombohedral structure of Bi leads to very different behavior of material parameters upon melting as compared with fcc metals. Therefore, our observation of the superheating of Bi(0001), together with the previously observed superheating of Pb(111), suggests the generality of the superheating phenomenon