Cherimolacyclopeptides are a class of cytotoxic cyclic peptides which exhibited significant activities against the human nasopharyngeal carcinoma cell culture system. The synthesis and study of cyclic peptide analogues presents a powerful move in the design and discovery of novel peptide drugs. Thus, the solid-phase syntheses of cherimolacyclopeptide E, cherimolacyclopeptide C, sansalvamide A, and the alanine-substituted analogues of cherimolacyclopeptide E were carried out in the present study. The synthetic cyclic peptides were then subjected to KB and MDA-MB-231 cell lines to examine the effect of side chain on the anticancer potential. The results indicated a significant enhancement in the activity of the analogues as compared to the parent peptide. The present study thus provides a new insight into peptide analogues and is especially useful for the scientific community involved in Solid-Phase Peptide Synthesis and anticancer activities or any one else who may be interested in alanine-scanning analogues.