1 Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.
2 Department of Chemistry and Biochemistry and Centre for NanoScience Research, Concordia University, Montreal, QC H4B 1R6, Canada.
3 Department of Materials Science and Engineering, University of Toronto, Toronto, ON M5S 3E4, Canada.

Kesterite Cu₂ZnSnS₄ (k-CZTS) nanocrystals have received attention for their tunable optoelectronic properties, as well as the earth abundance of their constituent atoms. However, the phase-pure synthesis of these quaternary NCs is challenging due to their polymorphism, as well as the undesired formation of related binary and ternary impurities. A general synthetic route to tackle this complexity is to pass through intermediate template nanocrystals that direct subsequent cation exchange toward the desired quaternary crystalline phase, particularly those that are thermodynamically disfavored or otherwise synthetically challenging. Here, working within this model multinary system, we achieve control over the formation of three binary copper sulfide polymorphs, cubic digenite (Cu_1.8S), hexagonal covellite (CuS), and monoclinic djurleite (Cu_1.94S). Controlled experiments with Cu⁰ seeds show that selected binary phases can be favored by the identity and stoichiometry of the sulfur precursor alone under otherwise comparable reaction conditions. We then demonstrate that the nature of the Cu_2-xS template dictates the final polymorph of the CZTS nanocrystal products. Through digenite, the cation exchange reaction readily yields the k-CZTS phase due to its highly similar anion sublattice. Covellite nanocrystals template the k-CZTS phase but via major structural rearrangement to digenite that requires elevated temperatures in the absence of a strong reducing agent. In contrast, we show that independently synthesized djurleite nanorods template the formation of the wurtzite polymorph (w-CZTS) but with prominent stacking faults in the final product. Applying this refined understanding to the standard one-pot syntheses of k- and w-CZTS nanocrystals, we identify that these reactions are each effectively templated by binary intermediates formed in situ, harnessing their properties to guide the overall synthesis of phase-pure quaternary materials. Our results provide tools for the careful development of tailored nanocrystal syntheses in complex polymorphic systems.