In recent years, much effort has been directed towards the development of new strategies for the efficient synthesis of libraries of peptidomimetics as potential therapeutic leads. The solid phase inverse synthesis of peptides(N(r)C) has only received a fraction of the attention given to the classical (C(r)N) solid phase assembly of peptides due to oxazolone-induced epimerisation. However, rather than trying to prevent its formation we have demonstrated how the peptide-derived 5(4H)-oxazolone can be used effectively as an ideal precursor to a range of peptidomimetics. (Fig. 9971) The development of a suitable strategy for the solid phase inverse synthesis of peptides is described and investigated as a valuable route into C-terminally modified peptides. This methodology is then applied to the construction of the polymer-supported 5(4H)-oxazolone II and various transformations thereof have been examined, often with solution phase comparisons.