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This is an image of an arrow sweeping each of the successive angles in the star. Notice that, after it traces all $5$ angles, its orientation is reversed - meaning it has rotated $180^{\circ}$ and that this must be the sum of the angles. We can do the same thing to the star in your figure, ergo, its angles too sum to $180^{\circ}$.
A Generalization:
We can do the same thing to a figure like this, whose angles sum to $180^{\circ}$:
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We can also do this to a triangle. The important property is this:
There must be no vertices of the star interior to the cone swept out by a ray traversing a given angle.
Satisfying this condition - which basically says that we never have to "ignore" vertices, but instead just rotate the arrow and see what it hits - we find that we can order the vertices in a "clockwise" manner, so that, at each angle, either the head or the tail of the arrow steps to the next vertex in the order (and they alternate which). Obviously, both head and tail will make a full revolution when twice as many angles as vertices have been traced, yielding the desired result.
(One might also express my condition as "assigning the vertices the numbers $1$ through $2n+1$ in clockwise order as seen from a central point, it must be that $1$ connects to $n$ and $n+1$, and all other points are connected analogously")