We have found diffusion of polyelectrolyte chains within multilayer films to be highly anisotropic, with the preferential chain motion parallel to the substrate. The degree of anisotropy was quantified by a combination of fluorescence recovery after photobleaching and neutron reflectometry, probing chain diffusion in directions parallel and perpendicular to the substrate, respectively. Chain mobility was controlled by ionic strength of annealing solutions and steric hindrance to ionic pairing of interacting polyelectrolytes.