Fix a *-orderable field k. We introduce the class of *-orderable semigroups as those semigroups with involution S for which the semigroup algebra kS endowed with the canonical involution admits a *-ordering. It is shown that this class is a quasivariety that is locally and residually closed. A cancellative nilpotent semigroup with involution is proved to be *-orderable if and only if it has unique extraction of roots. In general this equivalence fails, although every *-orderable semigroup has unique extraction of roots.