cos−1 is a function such that cos−1(t) is an angle x from [0;2π) such that cos(x)=t.
We know that cos(π/3)=1/2. Also from trigonometry cos(π−y)=−cos(y) for every real y.
Then
cos(π/3)=1/2=−cos(π−π/3)=−cos(2π/3)
cos(2π/3)=−1/2
Now we get for angle 2π/3 equality cos(2π/3)=−1/2. Then by definition cos−1(−1/2)=2π/3