The use of polyelectrolyte complexes (PECs) provides new opportunities for surface engineering of solid particles in aqueous environments to functionalize the solids either for use in interactive products or to tailor their adhesive interactions in the dry and/or wet state. This chapter describes the use of PECs in paper-making applications where the PECs are used for tailoring the surfaces of wood-based fibres. Initially a detailed description of the adsorption process is given, in more general terms, and in this respect both in situ formed and pre-formed complexes are considered. When using in situ formed complexes, which were intentionally formed by the addition of oppositely charged polymers, it was established that the order of addition of the two polyelectrolytes was important, and by adding the polycation first a more extensive fibre flocculation was found. PECs can also form in situ by the interaction between polyelectrolytes added and polyelectrolytes already present in the fibre suspension originating from the wood material, e.g. lignosulphonates or hemicelluloses. In this respect the complexation can be detrimental for process efficiency and/or product quality depending on the charge balance between the components, and when using the PECs for fibre engineering it is not recommended to rely on in situ PEC formation. Instead the PECs should be pre-formed before addition to the fibres. The use of pre-formed PECs in the paper-making process is described as three sub-processes: PEC formation, adsorption onto surfaces, and the effect on the adhesion between surfaces. The addition of PECs, and adsorption to the fibres, prior to formation of the paper network structure has shown to result in a significant increase in joint strength between the fibres and to an increased strength of the paper made from the fibres. The increased joint strength between the fibres is due to both an increased molecular contact area between the fibres and an increased molecular adhesion. The increased paper strength is also a result of an increased number of fibre/fibre contacts/unit volume of the paper network.