Abstract: Adding a complementary achiral monomer to polymers embedding a mixture of enantiopure monomers (the “sergeants”) and achiral monomers (the “soldiers”) is expected to decrease the optical purity of the polymer main chain. This study reports the influence of such achiral benzene‐1,3,5‐tricarboxamide (BTA) additives on the properties of “sergeants‐and‐soldiers” mixtures composed of an achiral BTA ligand coordinated to copper and of an enantiopure BTA monomer. Whilst N , N’ , N ’’‐tris(octyl)benzene‐1,3,5‐tricarboxamide ( BTA C8 ) shows no significant improvement in term of enantioselectivity in the catalytic reaction of reference, achiral BTA monomers derived from α,α’‐disubstituted amino esters all lead to an increase in the selectivity at low “sergeant” ratio. This different behaviour was probed by characterizing the coassemblies embedding BTA C8 , i. e. the worst‐performing achiral additive, and the BTA derived from the ester of 1‐aminocyclohexane carboxylic acid ( BTA Achc ), the best‐performing one. Both additives were found to efficiently intercalate with the ligand and the “sergeant” leading to the formation of single helices. However, only the terpolymer embedding BTA Achc appears to be homochiral, accounting for the good enantioselectivity even at very low “sergeant” ratio (0.25 %).