We studied the stratification behavior of free-standing foam films which are stabilized by nonionic surfactants and contain polyelectrolytes with different backbone flexibilities, namely sulfonated polyacrylamide (PAMPS), carboxymethyl-chitin (CM-Chitin), Xanthan, and DNA. Stratification is due to a specific arrangement of the polymer chains in the confined environment of the thin films. While stratification is easily observed for films containing PAMPS and CM-Chitin, it is more difficult to observe with Xanthan and DNA. We will discuss this effect in terms of different polymer backbone rigidities, which, in turn, are expected to lead to different time scales for polymer network relaxation.