I'm assuming that you have a finite-dimensional base Hilbert space $\mathcal H_0$ and that you're building your full Hilbert space as $\mathcal H=\mathcal H_0\otimes \mathcal H_0$. In these conditions, the set of separable states has measure zero.
(It gets a bit more complicated if you have $\mathcal H_0^{\otimes 4}$ and you're allowed to split it any way you want among those two factors, and the answer is negative if you're allowed to look for any tensor-product structure in your space, as you can always take one factor along your given $|\psi⟩$.)
Consider, then, a given basis $\{|n⟩:n=1,\ldots,N\}$ for $\mathcal H_0$, which means that any arbitrary state $|\psi⟩\in\mathcal H$ can be written as
$$
|\psi⟩=\sum_{n,m} \psi_{nm}|n⟩\otimes|m⟩.
$$
If, in particular, $|\psi⟩$ can be written as a tensor product $|\psi⟩=|u⟩\otimes|v⟩$, then you have
$$
|\psi⟩
=\left(\sum_n u_n |n⟩\right)\left(\sum_m v_m |m⟩\right)
=\sum_{n,m} u_nv_m |n⟩\otimes|m⟩;
$$
that is, the coefficient matrix $\psi_{nm}$ has the form $\psi_{nm}=u_n v_m$. This means that this matrix has rank one, which then means that it must have determinant equal to zero. Since the determinant is a continuous polynomial function $\det\colon \mathbb{C}^{N\times N}\to\mathbb C$, its zero set has Borel measure zero inside $\mathbb{C}^{N\times N}$, and therefore correspondingly inside $\mathcal H$.
This means, finally, that if you choose a random vector $|\psi⟩\in\mathcal H$ using a probability measure that is absolutely continuous with respect to the canonical Borel measure on $\mathcal H\cong\mathbb C^{N\times N}$, then it is almost certainly entangled. As an added bonus from exactly the same argument, such a vector will actually (almost certainly) have a full Schmidt rank.
A bit more intuitively, what this argument is saying is that separable states form a very thin manifold inside the full Hilbert space, and this is caught quite well by the spirit of zeldredge's answer. In particular, to describe an arbitrary separable state, you need $2N-1$ complex parameters ($N$ each for the components of $|u⟩$ and $|v⟩$, minus a shared normalization), so roughly speaking the separable states will form a submanifold of dimension $2N-1$. However, this is embedded inside a much bigger manifold $\mathcal H$ of dimension $N^2$, which requires many more components to describe, so for $N$ bigger than two the separable states are a very thin slice indeed.