Although there are many methods of fabricating nanofibres, electrospinning is perhaps the most versatile process. Materials such as polymer, composites, ceramic and metal nanofibres have been fabricated using electrospinning directly or through post-spinning processes. However, what makes electrospinning different from other nanofibre fabrication processes is its ability to form various fibre assemblies. This will certainly enhance the performance of products made from nanofibres and allow application specific modifications. It is therefore vital for us to understand the various parameters and processes that allow us to fabricate the desired fibre assemblies. Fibre assemblies that can be fabricated include nonwoven fibre mesh, aligned fibre mesh, patterned fibre mesh, random three-dimensional structures and sub-micron spring and convoluted fibres. Nevertheless, more studies are required to understand and precisely control the actual mechanics in the formation of various electrospun fibrous assemblies.