Alternating layers of cationic and anionic block copolymer micelles have been deposited onto colloidal silica particles using a layer-by-layer approach. The resulting films have been investigated using a number of characterization techniques including zeta potential measurements, dynamic light scattering, thermo-gravimetric analysis and microscopy. The micelles used here demonstrate pH-responsive behaviour both in solution and when adsorbed at interfaces. It has been shown that block copolymer micelles can selectively encapsulate and release hydrophobic materials; therefore, the incorporation of such responsive species within films has the potential to offer increased functionality. The formation of films onto colloidal particles is of great interest as it can provide pathways to direct encapsulation of materials along with surface modification. This study aims to provide new insights into the nature and properties of responsive films. Such studies will allow for the future development of novel delivery systems that have potential application within a number of industrial sectors including personal care products, pharmaceuticals and agro-chemicals.