Light-driven rotary molecular motors based on overcrowded alkenes have been firmly established in the pantheon of artificial molecular machines. Applications range far and wide, although the impact of these versatile compounds on our fundamental understanding of chirality and molecular motion cannot be underestimated. The development of molecules with such novel properties inevitably goes hand in hand with the exploration of novel analytical methods. To demonstrate and investigate the rotational properties of overcrowded alkene-based motors and switches, we must embrace innovative ways of using common lab equipment and branch out into learning new analytical techniques. In this chapter, we aim to provide a practical guide for the study of overcrowded alkene based molecular motors and switches. We commence with an overview of the most commonly used methods to characterize these compounds, and specifically focus on our collective experimental experience in investigating rotational and/or switching behavior. In addition, we will discuss various cutting-edge techniques that have recently facilitated even further investigation into the unique properties of these fascinating molecules.