Given that \( \vec{a} \) and \( \vec{b} \) are unit vectors:
\[
|\vec{a}| = 1 \quad \text{and} \quad |\vec{b}| = 1.
\]
It is also given that \( 2\vec{a} + 3\vec{b} \) is a unit vector, which implies:
\[
|2\vec{a} + 3\vec{b}| = 1.
\]
Using the formula for the magnitude of a vector:
\[
|2\vec{a} + 3\vec{b}|^2 = (2\vec{a} + 3\vec{b}) \cdot (2\vec{a} + 3\vec{b}).
\]
Expanding the dot product:
\[
|2\vec{a} + 3\vec{b}|^2 = 4|\vec{a}|^2 + 12 \vec{a} \cdot \vec{b} + 9|\vec{b}|^2.
\]
Substituting \( |\vec{a}| = 1 \) and \( |\vec{b}| = 1 \):
\[
|2\vec{a} + 3\vec{b}|^2 = 4 + 12 \vec{a} \cdot \vec{b} + 9 = 13 + 12 \vec{a} \cdot \vec{b}.
\]
Since \( |2\vec{a} + 3\vec{b}| = 1 \), we equate:
\[
13 + 12 \vec{a} \cdot \vec{b} = 1.
\]
Solving for \( \vec{a} \cdot \vec{b} \):
\[
12 \vec{a} \cdot \vec{b} = -12 \quad \Rightarrow \quad \vec{a} \cdot \vec{b} = -1.
\]
The dot product \( \vec{a} \cdot \vec{b} \) is related to the angle \( \theta \) between \( \vec{a} \) and \( \vec{b} \) as:
\[
\vec{a} \cdot \vec{b} = |\vec{a}| |\vec{b}| \cos \theta = \cos \theta.
\]
Substituting \( \vec{a} \cdot \vec{b} = -1 \):
\[
\cos \theta = -1 \quad \Rightarrow \quad \theta = \pi.
\]
Final Answer:
The angle between \( \vec{a} \) and \( \vec{b} \) is:
\[
\boxed{\theta = \pi \text{ radians.}}
\]