The overhead tricep extension works the tricep muscle, so it is a perfect exercise to include in an arm workout. You can perform this exercise with only your bodyweight, as shown in the video below. You can also use dumbbells, bands, or cable machines.
In any case the resistance starts behind your head and you extend your arms until they are completely straight. Activation of the core is important during this exercise to keep balance and stability. Unless your whole workout focusses on arms, this exercise should probably be done near the end. It is a secondary exercise that almost completely isolates the tricep muscles