Well, your thief has to actually hit something with it. I'm using Imoen, and at level 5 she still usually misses a backstab. Montaron would be good with this, assuming you're keeping an evil party. Furthermore, Kivan could use it. Granted, he doesn't get backstab damage, but (espec. with specialization), he can hit more often, and still do more damage, plus switch over to a better weapon once the enemy is poisoned.
On a side note, in the 2nd ed. rules, good characters are technically not allowed to use the dagger of venom...
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