Multi-component self-assembled systems can form highly ordered, complex architectures with diverse morphologies which can be utilized for various high-tech applications. Moreover, a combinatorial library approach can allow us to screen various backbones at the same time for tailoring the functionalities as desired. We report two series of multi-component salt-based gelators based on pivalic acid and tert-butylacetic acid (TBAA) using same set of amines. The two sets of compounds were scrutinized for their gelation performance in a variety of solvents and compared, in order to assess and validate the basic principles behind gelation behavior. The role of acid and effect of increasing a methylene group on the gelation behavior, rheological properties and morphology has been probed.