Taking a slant on xnor's idea, consider the velocity of any ant towards $O$. I'll use the standard figures for the internal angle of a regular pentagon and the radius of a circumscribed circle from wikipedia.
Name the vertices $A,B,C,D,E$ starting at the top and working clockwise, and let $\theta = \angle OAB$.
By symmetry, $\angle OAE$ is also $\theta$, so $\angle BAE = 2\theta = 3\pi/5$ (internal angle of a regular pentagon), i.e. $\theta = 3\pi/10$.
The velocity $V$ of $A$ towards $O$ is $S \cos \theta$, so the time $T$ taken for $A$ to reach $O$ is ${AO \over V} = {L \over 2 \sin (\pi/5)} \times {1 \over S \cos \theta}$ (using the formula for the radius of a circumscribed circle).
$$\therefore T = {L \over 2S \sin (\pi/5) \cos (3\pi/10)} = {L \over 2S \sin^2(\pi/5)} \approx 1.45L/S$$
As xnor observes, the ants spiral through an unbounded angle.
As $T$ and $S$ are finite, the total scalar distance $D=TS$ traversed by each ant is also finite. Since $T \approx 1.45L/S$ from before, we also have $TS \approx 1.45L$, i.e. $D \approx 1.45L$.
The counter-intuitive result hinted at by leoll2 is then the finite time taken to traverse an infinite spiral, where the total length of the spiral is a constant factor of about 1.45 times the length of one side of the initial pentagon.
Note: thanks to leoll2 for pointing out the trig simplification.