The key to controlling the fabrication process of transition metal sulfide nanocrystals is to understand the reaction mechanism, especially the coordination of ligands and solvents during their synthesis. We utilize in situ high-energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) as well as in situ valence-to-core X-ray emission spectroscopy (vtc-XES) combined with density functional theory (DFT) calculations to identify the formation of a tetrahedral [Zn(OA)4]2+ and an octahedral [Zn(OA)6]2+ complex, and the ligand exchange to a tetrahedral [Zn(SOA)4]2+ complex (OA = oleylamine, OAS = oleylthioamide), during the synthesis of ZnS nanorods in oleylamine. We observe in situ the transition of the electronic structure of [Zn(SOA)4]2+ with a HOMO/LUMO gap of 5.0 eV toward an electronic band gap of 4.3 and 3.8 eV for 1.9 nm large ZnS wurtzite nanospheres and 2 × 7 nm sphalerite nanorods, respectively. Thus, we demonstrate how in situ multimodal X-ray spectroscopy and scattering studies can not only resolve structure, size, and shape during the growth and synthesis of NPs in organic solvents and at high temperature but also give direct information about their electronic structure, which is not readily accessible through other techniques.