A range of long chain alpha-olefins were prepared which contained amide (four examples) or ester (five examples) linkages. The olefins were copolymerized with maleic anhydride and the alternating copolymers produced were subjected to ring-opening reactions at the anhydride residues to give polymers containing acid-ester, acid-acid or acid-amide head groups. Monolayers of these polymers on water were studied and, in favourable cases, thick Langmuir-Blodgett multilayers were prepared. The latter were studied by X-ray reflectivity. The results obtained were compared with those obtained from analogous polymers prepared starting from the simple alpha-olefins undecene, octadecene and tricosene. The polymers prepared from the alpha-olefins containing amide linkages generally gave poor monolayers and in only one case could a Langmuir-Blodgett multilayer be prepared. The polymers prepared from the alpha-olefins containing ester linkages generally gave better monolayers, especially if the ester group was shielded from solvation either by being surrounded with lipophilic chains or by virtue of being a t-butyl ester or an ester of an aromatic acid, or because the ester was linked to a mesogenic group. Several of the latter polymers gave excellent Langmuir-Blodgett firms. In general polymers with acid-acid head groups gave better films than the analogues with acid-methyl ester head groups.