It is more than a decade that Ionic Polymer-Metal Composites (IPMCs) have been known as an exciting class of smart materials and attracted growing worldwide attention. IPMCs are soft and flexible, and can generate large and reversible strains in response to electrical stimulus. Thus, they have potential applications in industrial and biomedical fields, as actuators. Before these applications can be realized , however, the performance of IPMCs must be understood and improved through improvement of component characteristics and of preparation methods. In general, the aim of this thesis is to gain a fundamental understanding of the chemical and structural factors that affect the electromechanical performance of IPMCs. To this end, a multi-technique investigation is applied to correlate the electrochemical and electromechanical behavior of IPMCs, during operation, with their chemistry, microstructure and nanostructure. Researchers have suggested several plausible mechanical and mathematical models to reveal that ion transport occurs within IPMCs and that it is an important factor in their actuation performance. However, there is still a need for further experimental studies to help refine our understanding of the actuation mechanism of these materials. In this work, the powerful, non-invasive and non-destructive technique of Magnetic Resonance Imaging (MRI) is employed to study the internal structure and water content distribution in Nafion membranes and also IPMCs. Moreover, MRI is also applied to image electrically-induced diffusion of ions with their associated water molecules in real time, in operating IPMC actuators. This forms the major part of this project and, to the best of our knowledge, it is the first recorded electrochemical experiment of this kind. The size and dimensions of IPMCs can affect their actuation performance. Thus, in this work, model IPMC actuators are prepared based on the available commercial Nafion membrane and fabricated cast Nafion membrane and their electromechanical behaviors are compared. The effect of parameters such as electrode composition and Nafion thickness on actuation behavior is also studied by measuring displacement and force generation of the IPMC actuators during actuation cycles. Simultaneous current and electrochemical measurements are made to correlate electrochemical processes with actuation behavior directly. Scanning electron microscopy (SEM) is also used to study the internal and surface structure of IPMCs.