A series of poly(benzyl vinyl ether)s of low molecular weight (5000 to 15000 g mol(-1)) and narrow molecular distribution (($) over bar M(w)/($) over bar M(n) < 1.20) have been synthesised via the cationic polymerisation of benzyl vinyl ether. Acetylation with acetic anhydride/tin (IV) chloride leads to poly(vinyl acetate), which can be hydrolysed to near-monodisperse water-soluble poly(vinyl alcohol) with an isotacticity of approximately 47%. This polymer was re-acetylated and its molecular weight distribution assessed to confirm that hydrolysis gives minimal chain scission.