Is there a general characterization, or classification, of electrostatic fields whose field lines are straight?
I had a previous answer (and some other still present answers) that related to the curvature with the expression depending upon something like $\left( \mathbf{E} \cdot \nabla \right) \mathbf{E}$ which only works for divergenceless fields.
The part I had missed is that I left the expression in terms of the magnitude of the field instead of using the unit vectors. So let's define a unit vector as $\hat{u} = \tfrac{ \mathbf{V} }{ \lvert \mathbf{V} \rvert }$ then we can define curvature in terms of this as:
$$
\boldsymbol{\kappa}_{c} = \left( \hat{u} \cdot \nabla \right) \hat{u} \tag{0}
$$
The radius of curvature is just the inverse of the magnitude of the curvature given by:
$$
\rho_{c} = \frac{ 1 }{ \lvert \boldsymbol{\kappa}_{c} \rvert } \tag{1}
$$
A field line that is straight will satisfy $\rho_{c} \rightarrow \infty$, i.e., a zero magnitude curvature.
Example: Point Charge
For a point charge, the electric field $\hat{u} = (1,0,0)$ in spherical coordinates and so that Equation 0 goes to zero. If we use the full electric field vector $\mathbf{E} \propto r^{-2} \hat{r}$ in place of $\hat{u}$ then Equation 0 would not be zero, which was my the with my previous answer and the issue with some of the other answers herein.
Example: Linear Gradient
Suppose we a linearly increasing (in magnitude) electric field given by:
$$
\mathbf{E} = E_{o} \left( 1 + z \right) \hat{x} \tag{2}
$$
Again if we use $\mathbf{E}$ instead of its unit vector, Equation 0 will not have a zero magnitude but it will if we use the unit vector.
Example: Dipole
Suppose we have a dipole made of two point charges separated by some vector $\mathbf{d}$ and we observe said field at some displacement $\mathbf{r}$ in the $\phi = 0$ plane. Then the electric field will have an $r$ and $\theta$ component given by:
$$
\mathbf{E} \simeq \frac{ k \ d }{ r^{3} } \left[ \left( 2 \ \cos{\theta} \right) \hat{r} + \sin{\theta} \ \hat{\theta} \right] \tag{3}
$$
We know the fields are not straight here and indeed the expression for Equation 0 is not zero but a complex function of $r$, $d$, and $\theta$ given by:
$$
\begin{align}
\left( \left( \hat{e} \cdot \nabla \right) \hat{e} \right)_{r} & = - \frac{ 8 \sin^{2}{\theta} }{ r \left( 5 + 3 \cos{2 \theta} \right)^{2} } \tag{4a} \\
\left( \left( \hat{e} \cdot \nabla \right) \hat{e} \right)_{\theta} & = \frac{ 8 \sin{2 \theta} }{ r \left( 5 + 3 \cos{2 \theta} \right)^{2} } \tag{4b} \\
\left( \left( \hat{e} \cdot \nabla \right) \hat{e} \right)_{\phi} & = 0 \tag{4c}
\end{align}
$$
where $\hat{e} = \tfrac{ \mathbf{E} }{ \lvert \mathbf{E} \rvert }$ is the electric field unit vector given by:
$$
\begin{align}
e_{r} & = \frac{ 2 \cos{\theta} }{ \sqrt{ 4 \cos^{2}{\theta} + \sin^{2}{\theta} } } \tag{5a} \\
e_{\theta} & = \frac{ \sin{\theta} }{ \sqrt{ 4 \cos^{2}{\theta} + \sin^{2}{\theta} } } \tag{5b} \\
e_{\phi} & = 0 \tag{5c}
\end{align}
$$
Answer
Therefore, the field line curvature must be calculated in terms of the unit vector of the field, not the field with its magnitude included. In the limit of $\rho_{c} \rightarrow \infty$, the field lines will always be straight (ignoring critical points where the magnitude is zero).