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Chiral building blocks have the ability to self-assemble and transfer chirality to larger hierarchical length scales, which can be leveraged for the development of novel nanomaterials. Chiral block copolymers, where one block is made completely chiral, are prime candidates for studying this phenomenon, but fundamental questions regarding the self-assembly are still unanswered. For one, experimental studies using different chemistries have shown unexplained diverging shifts in the order–disorder transition temperature. In this study, particle-based molecular simulations of chiral block copolymers in the disordered melt were performed to uncover the thermodynamic behavior of these systems. A wide range of helical models were selected, and several free energy calculations were performed. Specifically, we aimed to understand (1) the thermodynamic impact of changing the conformation of one block in chemically identical block copolymers and (2) the effect of the conformation on the Flory–Huggins interaction parameter, χ, when chemical disparity was introduced. We found that the effective block repulsion exhibits diverging behavior, depending on the specific conformational details of the helical block. Commonly used conformational metrics for flexible or stiff block copolymers do not capture the effective block repulsion because helical blocks are semiflexible and aspherical. Instead, pitch can quantitatively capture the effective block repulsion. Quite remarkably, the shift in χ for chemically dissimilar block copolymers can switch sign with small changes in the pitch of the helix.