Vanilla Hermetic Magic, particularly in 5th edition, is not well suited to "indirect" mind control effects. In general, you can cast a Mentem effect on the barmaid so she won't be attracted to the hero, but you can't cast the effect on the hero so he'll repel every barmaid he encounters. Incidentally, the Technique involved is not necessarily Rego. It could be Muto (changing any romantic feeling into a related one of plain friendship), or Perdo (just destroying any romantic feeling).
There are, however, some workarounds.
The most obvious is to summon some appropriate spirit and let it take care of the issue. This can be an airy spirit (well within the power of vanilla Hermetic Magic), or for some magi with access to theurgic effects, an appropriate daimon. Merinita magi with the mystery of the Anima can instead call upon minor faeries to the same result.
A somewhat more subtle nudge would be a variation on Aura of Ennobled Presence (see the Tytalus chapter in HoH:S for examples), to make the hero more homely, forcing upon him a -3 on all rolls to seduce appropriately compatible characters. A sneakier alternative would be a PeMe or ReMe (or Re(Pe)Me) effect that makes the hero subtly worse at seduction either by impairing his ability to seduce (see HoH:S p.66-67), or nudging him towards projecting a friend-not-lover attitude (perhaps impairing his perception of the issue). None of these methods is foolproof, of course: the hero could always encounter a barmaid who somehow falls in love with him despite seeing him as a homely guy utterly incapable of seduction and completely uninterested in romance.
A blunt solution would of course be the Phantom Gift. That certainly makes seduction almost impossible on most barmaids, but the hero won't be perceived as a friend either.
Of course, a magus who's sufficiently upset with the hero and willing to spend the time, can keep track of his love interests from afar with appropriate Intellego magics, and slap onto any Room he happens to share with such a person an appropriate Mentem effect, either at R:Arc or through a Wizard Tunnel. Or the magus could "hang" on the hero such an effect with a Waiting Spell or variation thereof, perhaps triggered by the aforementioned Intellego magics.
Finally, I'd rank such a "Friendzone curse" as a Minor Flaw (not quite a Story Flaw, because it does not really generate Stories like Curse of Venus does). In principle, if a magus warps a mundane character enough, said character will acquire Flaws from the Warping, and these will be "appropriate" to the source of Warping. It's ultimately up to the troupe to decide if a magus can, with sufficient preparation and/or Finesse, tailor the generic Warping inflicted by CrVi effects (or, simply, sufficiently long-lasting and/or high-level magics) so that it produces the desired Flaw. My troupe probably would not allow this to happen reliably as it can be abused, but it could certainly happen accidentally, e.g. as a result of the hero being subjected repeatedly to other barmaid-repellant magics.