Metal-mediated growth provides an effective route to high-quality hexagonal boron nitride (hBN), but hBN formation on the metal does not necessarily ensure hBN formation on an adjoining dielectric substrate. Here, we investigate this distinction using a vertically stacked Ni–Cr/boron/sapphire configuration operated at 1550~^∘C under atmospheric pressure, with the relative boron supply varied at fixed Ni:Cr = 8:2. hBN is detected by Raman spectroscopy on the gas-exposed alloy surface throughout the investigated Alloy:B range, whereas sapphire-side hBN appears only at the higher relative boron supplies of Alloy:B = 24:1 and 18:1, as confirmed by both Raman spectroscopy and XRD. The hBN (002) reflection further narrows as the boron supply increases from 24:1 to 18:1, corresponding to an increase in the apparent c-axis coherent length from approximately 86 to 143 nm. Additional crystalline reflections also emerge only under these higher-boron conditions. These results identify boron supply as a key parameter governing the transition from alloy-side hBN formation to concurrent sapphire-side hBN growth. Once formed, sapphire-side hBN occurs within a substantially reconstructed and chemically modified Al/O-rich sapphire environment rather than as a uniform film on an intact substrate. To our knowledge, this study provides the first demonstration of successful sapphire-side hBN formation by Ni–Cr-mediated growth.