Self-assembled structures adsorbed on carbon nanotubes and other nanofibres offer a plethora of opportunities to endow them with new functions and to integrate them into devices and materials. At the same time they are key to solve the greatest problem in carbon nanotube utilisation—debundling and individualisation. Success will inevitably require an understanding of the underlying structure–function relationship of the adsorbed surfactant layer. Computer simulations are ideally suited to develop this understanding as they enable us to study the structure–function relationship in great detail. Combining the results from mesoscale and atomistic simulations we begin to develop this understanding and derive a number of recommendations for optimal dispersion design.