The generation of peralkylated peptidomimetic combinatorial libraries can be accomplished by applying a 'libraries-from-libraries' concept. The chemical modification of existing resin-bound tri- and tetrapeptide libraries through amide N-alkylation creates libraries having different physical, chemical, and biological properties. The synthetic methods used to produce these peralkylated compounds with different alkylating reagents, such as methyl iodide, allyl bromide, and benzyl bromide, are described.