The familiar role of tocols (tocopherols and tocotrienols) as lipid-soluble chain-terminating inhibitors of lipid peroxidation is currently in the midst of a reinterpretation. New biological activities have been described for tocols that apparently are not dependent on their well-established antioxidant behaviour. These activities could well be real, but there remain large gaps in our understanding of the behaviour of tocols in membranes, especially when it comes to the alpha-, beta-, gamma-, delta-chroman methylation patterns and the seemingly special nature of tocotrienols. It is inappropriate to make conclusions and develop models based on in vivo (or cell culture) results with reference to in vitro measurements of antioxidant activity. When present in biological membranes, tocols will experience a large variation in the local composition of phospholipids and the presence of neutral lipids such as cholesterol, both of which would be expected to change the efficiency of antioxidant action. It is likely that tocols are not homogeneously dispersed in a membrane, but it is still not known whether any specific combination of lipid head group and acyl chains are conferred special protection from peroxidation, nor do we currently appreciate the structural role that tocols play in membranes. Tocols may enhance curvature stress or counteract similar stresses generated by other lipids such as lysolipids. This review will outline what is known about the location and behaviour of tocols in phospholipid bilayers. We will draw mainly from the biophysical literature, but will attempt to extend the discussion to biologically relevant phenomena when appropriate. We hope that it will assist researchers when designing new experiments and when critically assessing the results, in turn providing a more thorough understanding of the biochemistry of tocols.