Langmuir–Blodgett methods are perhaps the original approach for achieving controlled deposition of organic thin films. Molecules are first organized into a monolayer array on the surface of water before transfer as a monolayer onto solid supports. Molecular monolayers, multilayers, and multilayered heterostructures can be achieved. The capability of exercising such control over thin film assemblies has attracted materials chemists and physicists to develop Langmuir–Blodgett films for studies on organic conductors, magnets, non-linear optics, rectifiers, and intermolecular electron transfer. This article reviews objectives in each of these areas and selects some specific examples from the literature to highlight the state of the art, mostly from the point of view of the chemical systems that are studied. Mixed organic/inorganic hybrid films represent a new direction for Langmuir–Blodgett films in materials science, combining conventional inorganic solid-state phenomena with the properties of the organic networks, and recent examples, taken principally from the authors' work, are highlighted.