Single-phased and dual-emissive nanocrystals with broad emission are attractive fluorescent materials for optoelectronic devices due to their unique properties. Until now, the effect of different metallic cations and inorganic anions on III-V group quantum dots (QDs) concerning luminescence features and crystalline growth has been less explored. In this work, dual-emissive InP/ZnS QDs single-doped with transition-metal compounds (Cu2+, Ag+, or Mn2+) are synthesized to compare their optical and morphological properties. The corresponding doping concentrations to realize dual emission with comparative intensity for Cu, Ag, and Mn are 0.8, 6, and 80%, which vary greatly and might be attributed to different precursor reactivities. As for the morphological and internal structures, transmission electron microscopy (TEM) images indicate that transition-metal ions have no obvious effect on the morphological properties and a higher concentration of chloride anions binding with an In-rich interface could conduce to a homogeneous distribution and triangular growth through the comparison of different metal chlorides as precursors. X-ray photoelectron spectroscopy (XPS) results further demonstrate that the high-resolution In 3d spectrum of Mn-doped InP/ZnS QDs with MnCl2 is mainly dominated by In-P bonds, indicating fewer intermediate chemical states. These results concerning well-defined InP/ZnS QDs could promote more diverse insight into surface chemistry and help to better understand the growth mechanism, thus making it possible to regulate InP/ZnS QDs into desired formats for different practical applications like white light-emitting diodes (LEDs).