Coordination multilayers consisting of Pd(II) pincer-type complexes and poly(vinyl pyridine) were synthesized and characterized. Film properties were found to be dependent on and could be tuned by varying bath deposition concentrations, polymer molecular weight, and solution additives that compete with binding. Generally, smoother, thinner films were obtained with lower poly(vinyl pyridine) deposition bath concentrations. Likewise, film thickness and roughness could be reduced by employing a higher-molecular-weight poly(vinyl pyridine). Film properties could also be influenced by using acetonitrile as a solution additive, effectively driving the binding equilibrium slightly toward the free species.