Due to their unique catalytic, electronic, and redox processes, Ni5P4 and NiP2 nanoparticles are of interest for a wide-range of applications from the hydrogen evolution reaction to energy storage (batteries); yet synthetic approaches to these materials are limited. In the present work, a phase-control strategy enabling the arrested-precipitation synthesis of nanoparticles of Ni5P4 and NiP2 as phase-pure samples using different Ni organometallic precursors and trioctylphosphine (TOP) is described. The composition and purity of the product can be tuned by changing key synthetic levers, including the Ni precursor, the oleylamine (OAm) coordinating solvent and TOP concentrations, temperature, time, and the presence or absence of a moderate temperature soak step to facilitate formation of Ni and/or Ni-P amorphous nanoparticle intermediates. Notably, the 230 °C intermediate step favors the ultimate formation of Ni2P and hinders further phosphidation to form Ni5P4 or NiP2 as phase-pure products. In the absence of this step, increasing the P/Ni ratio (13-20), reaction temperature (350-385 °C), and time (10-48 h) favors more P-rich phases, and these parameters can be adjusted to generate either Ni5P4 or NiP2. The phase of the obtained particles can also be tuned between pure Ni2P to Ni5P4 and NiP2 by simply decreasing the OAm/TOP ratio and/or changing the nickel precursor (nickel(II)acetylacetonate, nickel(II)acetate tetrahydrate, or bis(cyclooctadiene)nickel(0)). However, at high concentrations of OAm, the product formed is the same regardless of Ni precursor, suggesting the formation of a uniform Ni intermediate (an Ni-oleylamine complex) under these conditions that is responsible for product distribution. Intriguingly, under the extreme phosphidation conditions required to favor Ni5P4 and NiP2 over Ni2P (large excess of TOP), the 20-30 nm crystallites assemble into supraparticles with diameters of 100-500 nm. These factors are discussed in light of a comprehensive synthetic scheme utilized to control P incorporation in nickel phosphides.