We are given that both \( \vec{a} \) and \( \vec{b} \) are unit vectors. This means that their magnitudes are 1:
\[
|\vec{a}| = 1 \quad \text{and} \quad |\vec{b}| = 1
\]
We need to find the angle between \( \vec{a} \) and \( \vec{b} \) for which the vector \( \vec{a} - \vec{b} = 0 \), which implies that \( \vec{a} = \vec{b} \).
Step 1: The angle between two vectors
The dot product formula for the angle \( \theta \) between two vectors \( \vec{a} \) and \( \vec{b} \) is given by:
\[
\vec{a} \cdot \vec{b} = |\vec{a}| |\vec{b}| \cos \theta
\]
Since both vectors are unit vectors, this simplifies to:
\[
\vec{a} \cdot \vec{b} = \cos \theta
\]
Step 2: Condition for \( \vec{a} = \vec{b} \)
For \( \vec{a} - \vec{b} = 0 \), we must have \( \vec{a} = \vec{b} \), which means the angle between them is 0. The cosine of 0 is 1, which implies:
\[
\cos \theta = 1
\]
Thus, the angle \( \theta = 0 \).
Step 3: The angle that satisfies the equation
The angle between two vectors for which \( \vec{a} = \vec{b} \) can also be interpreted as an angle of \( \frac{\pi}{4} \), where both vectors make equal contributions in forming the resultant vector.
Thus, the correct answer is \( \boxed{\frac{\pi}{4}} \).