The seamless coalescence of parallelly aligned 2D materials is the primary route toward the synthesis of wafer-scale single crystals (WSSCs) of 2D materials. The epitaxial growth of various 2D materials on a single-crystal substrate, which is an essential condition of the seamless coalescence approach, has been extensively explored in previous studies. Here, by using hexagonal boron nitride (hBN) growth on a liquid gold surface as an example, we demonstrate that growth of WSSCs of 2D materials via the seamless coalescence of self-aligned 2D islands on a liquid substrate is possible. Here we show that, in the presence of hydrogen, all the hBN edges tend to be hydrogen terminated and the coalescence of hBN islands occurs only if their crystallographic lattices of neighboring hBN islands are aligned parallelly. The mechanism of hBN self-alignment revealed in this study implies that, under the optimum experimental condition, the seamless coalescence of 2D materials on a liquid substrate is possible and thus provides guidance for synthesizing WSSCs of various 2D materials by using liquid phase substrates.