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Make the assassin bring back a specific object such as a signet ring, a wizard's bonded item, the target's nose or whatever. Either as proof, or because the employer just happens to be weird. Easy pickings: the target is probably a level 6 expert or something like that.
Then have another assassin (hired by someone else) appear at the scene of the crime, and try to get the same object. Only one can get the spoils; no sharing. Were either of them prepared to fight each other? Bonus points if the target is not dead yet, and attempts to flee while the assassins are fighting each other. Extra points if you leave the competing assassin dead on the scene without leaving evidence of your own visit.
Unknown to the employer (or perhaps the employer just didn't tell you), the target is under observation of the city watch, a criminal gang, intellect devourers looking for a host, or whatever.
When the your player suddenly inhumes the poor NPC, a stake-out team gets very angry that all their hard work is suddenly wasted. Fortunately for them, there is a black-clad PC for them to interrogate, liquidate, or use as a corpsemobile. Cue chase.
The target has a dangerous disease. For some reason he cannot be cured or the infection cannot be publicized (perhaps the target is the head of the local church, and nobody can know that he has fallen from grace and can no longer cure himself), and has to be eliminated swiftly. Killing is easy, being infected may cause some complications. This is relatively easy to counter with access to healing magic, though.
This ploy is only useful if the backstory is sensible. Depending on the local access to healing, players may think it is absolute nonsense.