Certainly, $\frac{2}{3}$ is in smallest possible terms despite $2$ being even and $3$ being odd.
The point in this proof however that they are trying to make is that given that $a$ and $b$ are both natural numbers if we were to assume that $3b^2=a^2$ we have that if at least one of the two are even then both must be even and that if at least one of them is odd that both must be odd. This has to do with this equation and does not directly have to do with that $\frac{a}{b}$ is in simplest terms. Notice that if exactly one of the two is even and the other is odd then we would have an even number equal to an odd number which is impossible.
We notice then that if we were to assume that $a$ and $b$ are both even then we run into the issue of $\gcd(a,b)\geq 2$ as $2$ would be a common divider, contradicting that $\frac{a}{b}$ was in simplest terms. This implies then that $a$ and $b$ both cannot be even, and coupling with the earlier observation that we cannot have exactly one of them even and the other odd, this implies that both must be odd.
The proof continues as written.
Really, this step about them both being odd is unnecessary to begin with. We could have directly appealed to the fact that since $3b^2=a^2$ that $3\mid a^2$. Since $3$ is prime this implies that $3\mid a$. Similarly we can then show that $3\mid b$, arriving at our contradiction directly.