The area of colloidal photonic crystal research has attracted enormous attention in recent years as a result of the potential of such materials to provide the means of fabricating new or improved photonic devices. As an area where chemistry still predominates over engineering the field is still in its infancy in terms of finding real applications being limited by ease of fabrication, reproducibility and ‘quality’- for example the extent to which ordered structures may be prepared over large areas. It is our contention that the Langmuir-Blodgett assembly method when applied to colloidal particles of silica and perhaps other materials, offers a way of overcoming these issues. To this end the assembly of silica and other particles into colloidal photonic crystals using the Langmuir-Blodgett (LB) method is described and some of the numerous papers on this topic, which have been published, are reviewed. It is shown that the layer-by-layer control of photonic crystal growth afforded by the LB method allows for the fabrication of a range of novel, layered photonic crystals that may not be easily assembled using any other approach. Some of the more interesting of these structures, including so-called heterostructured photonic crystals comprising of layers of spheres having different diameters are presented and their optical properties described. Finally, we offer our comments as to future applications of this interesting technology.