Here's an example based on entanglement witnesses. Let
$$
|\psi\rangle=\frac{1}{\sqrt{2}}(|000\rangle+|111\rangle).
$$
The aim is to define an operator $W$ such that $\text{Tr}(W\rho_\text{sep})\geq 0$ for all separable states $\rho_\text{sep}$. That means for any $\rho$ such that $\text{Tr}(W\rho)<0$, it must be entangled.
An easy way to define such an operator is
$$
W=\alpha I-|\psi\rangle\langle\psi|,
$$
where
$$
\alpha=\max_{\rho_\text{sep}}\langle\psi|\rho_\text{sep}|\psi\rangle.
$$
In this particular case, the maximisation is achieved with $\rho_\text{sep}=|0\rangle\langle 0|^{\otimes 3}$, I believe, so $\alpha=\frac12$.
Of course, $\text{Tr}(W|\psi\rangle\langle\psi|)=\alpha-1=-\frac12$, so we see that it's entangled.
Now consider any other state $\rho$. We can think of the value $\text{Tr}(W\rho)$ as measuring distance. The smallest possible value is $-\frac12$, and if you have that, you've got the state $|\psi\rangle$. The larger the value, there is a sense of getting further away from $|\psi\rangle$. Now, the maximum value of $\text{Tr}(W\rho)$ is $\alpha=\frac12$, which is achieved by $\langle\psi|\rho|\psi\rangle=0$. So this categorises the states that are furthest away according to this specific measure. There are separable states which are orthogonal to $|\psi\rangle$, such as $|001\rangle$, and so they can be considered the furthest separable states.