PAMAMs make up the most ubiquitous family of dendrimers in use today, with their NH₂ surface functionality rendering them an excellent choice for several valuable applications. However, impurities introduced during synthesis and their surface functionality present unique challenges for analysis. In this work, we discuss and review the applicability of a range of analytical techniques and present methodologies to analyze PAMAM dendrimers from generation 0−7, to extract both chemical and size-based information, through these data, we clearly show how molecular weight and size grow through the generations. Additionally, we show how the shape factor changes from close to 1 in low generations, indicating a majority of mass in the shell of the system, to values around 0.75, indicating uniformly distributed mass across the system. We further highlight where challenges in analysis can occur, and strategies that can be employed to yield optimum results. These results are then explored in the context of the analytical systems employed, in a first-of-its-kind study to provide guidance on the best systems to choose for a variety of analytical applications.