Langmuir-Adam trough studies have been carried out to study the behavior of seven cyclic and linear short-chain small-molecule phosphazenes and four high polymers at air-water interfaces. The small-molecule compounds are models for a variety of phosphazene high polymers. The influence of phenoxy, 1,2-benzenedioxy, OCH2CF3, NH2, NEt(2), NBu(2), and OCH2CH2CH2CH2OCH3 side groups was studied. The air-water interface behavior of the small molecules depended on (a) the cyclic or linear skeletal structure and (b) the types of side groups linked to the ring or chain. The utilization of these results for understanding the behavior of phosphazene high polymers at air-water interfaces is discussed.