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Consider your own ability and reaction. Macerate tiny fish. Knock the fish unconscious (optional). Decapitate the fish. Pith the brain immediately.
These methods are only humane if you can perform them accurately and quickly. Skip to a different section if you think the sight of gore or a struggling fish will affect you. These methods are usually used to kill food fish or laboratory research subjects, not family pets. Unless you're experienced with fish anatomy, practice on dead fish first so you can perform these quickly and without mistakes. Fish less than 2 cm ( inch) long can be killed instantly in a fish macerator, which chops it apart with rapidly moving blades. Make sure to use a macerator intended for exactly your size of fish. The larger the fish is, the less humane this death is. Even if you have a macerator intended for larger fish, it may cause suffering. Stun the fish by clubbing it just above the eyes, with an appropriately sized, hard object. Repeat with more force if the fish is still conscious. There is evidence that at least some fish species can remain conscious after decapitation, so this step is highly recommended. Fish species adapted for low oxygen conditions are more likely to remain conscious after decapitation. Hold down the head and sever it with a powerful motion from a sharp knife, just behind the skull. Alternatively, you can insert the knife behind the skull and sever the spinal cord and vertebrae. This "cervical transection" is less messy, but not recommended unless you have experience with fish anatomy. Even after decapitation, the fish may still be alive for a short time. Ensure a rapid death by immediately inserting a sharp spike or knife into the brain, between the eyes. Push forward and backward to destroy the brain and the end of the spinal cord. You can use online resources to locate the most effective point to insert the spike, for various edible species.