The assembly and degradation behavior of oligoelectrolyte multilayer films (OEMs) self assembled by layer-by-layer deposition of positively and negatively charged oligoelectrolytes 1-6 was investigated. Next to colorless oligoelectrolytes we have employed representatives involving chromophores, in particular porphyrins. This allows for the systematic observation of both assembly and disassembly of the OEMs using optical spectroscopy, where chromophore containing building blocks serve as reporter electrolytes. The OEMs investigated in this study were built in a consistent, monomolecular matter and show linear correlation between the absorption and the number of layers. Using the concept of reporter electrolytes we have introduced for the first time also the use of non-chromophoric oligoelectrolytes, such as the new synthesized cationic system 2 as building blocks for OEMs. Moreover, we have investigated for the first time the degradation behavior of OEMs. We demonstrated that two different mechanisms of degradation proceed at the same time. The direct degradation is accompanied by a second release mechanism.