The mechanism of the transition from a continuous morphology to a porous morphology within polyelectrolyte multilayers (PEMs) of linear poly(ethylene imine) (LPEI) and poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) and PAA assembled by the layer-by-layer (LbL) technique is examined. These morphological changes were created by both acidic and basic postassembly treatments. Basic postassembly treatment is shown to create different types of porosity than acidic postassembly treatment. The morphological variation from the introduction of porosity to the collapse of these porous structures and the dissolution of films under postassembly treatments was observed by AFM, optical microscopy, quartz crystal microbalance (QCM), and SEM. These morphological transitions which are a result of structural rearrangement of weak polyelectrolytes due to pH changes are closely related to the neutralization of the polycations and the ionization of polyanions. Results obtained from FTIR spectroscopy and QCM confirm that polyelectrolytes are being selectively or partially released from the polyelectrolyte multilayers thin films (PEMs) in response to the pH treatment as a function of exposure time. In conclusion, here new information is presented about the structural reorganization found in a number of weak polyelectrolyte systems. This information will be useful in designing functional materials based on polyelectrolytes.