Physical vapor deposited two-dimensional (2D) materials span larger areas compared to exfoliated flakes, but suffer from very small grain or domain sizes. In this letter, we fabricate freestanding molybdenum disulfide (MoS2) and amorphous boron nitride (BN) specimens to expose both surfaces. We performed in situ heating in a transmission electron microscope to observe the domain restructuring in real time. The freestanding MoS2 specimens showed up to 100× increase in domain size, while the amorphous BN transformed in to polycrystalline hexagonal BN (h-BN) at temperatures around 600 °C much lower than the 850–1000 °C range cited in the literature.