The interactions between two macroscopic surfaces approaching one another underlies many of the phenomena observed in Colloid and Interface science. In Russia this gave rise to the branch of colloid science now referred to as Surface Forces. Important discoveries, such as the molecular organization of solvent molecules at an interface, have been unveiled by surface force measurements. More recently, forces and structures at macromolecular length scales have been uncovered. In particular, oscillatory force profiles have been detected from aqueous solutions containing polyelectrolytes. The force¯structure relationship can reflect organization in the bulk solution or the internal structure of the adsorbed layer. Using a range of surface force techniques, combined with X-ray and neutron scattering results, we review the main features of these fascinating systems and provide an overview of how they relate to other systems such as micellar solutions, polymer¯surfactant complexes and simple solvents.