Organic monolayers play a key role in many areas of science, including atmospheric chemistry, the shape-controlled growth of nanostructures, and as model biological membranes, to name a few. This is in part due to the nature of their intermolecular forces and their interactions with various substrates, which afford conformational flexibility and high degrees of order. I will describe our efforts to understand the structure and dynamics of a range of organized organic monolayers using nonlinear optical spectroscopy, scanning probe microscopy and other materials characterization methods. In so doing, I will show how even subtle changes in film chemistry at the microscopic level can lead to significant changes in the macroscopic physical properties of mono-and multilayer film architectures. Engineering specific functionality into monolayers allows one to construct model organic semiconducting and conducting polymeric monolayers that can provide fundamental insight into the nature of their electronic structure. Temperature dependent vibrational spectroscopy of monolayers provides insight into their low temperature phase behaviour and that of water confined in these films, which show signatures of homogeneous nucleation at 150 K!