It is shown that on Pt(111) it is possible to prepare hexagonal boron nitride (h‐BN) and graphene (G) in‐plane heterojunctions from a single molecular precursor, by thermal decomposition of dimethylamine borane (DMAB). Photoemission, near‐edge X‐ray absorption spectroscopy, low energy electron microscopy, and temperature programmed desorption measurements indicate that the layer fully covers the Pt(111) surface. Evidence of in‐plane layer continuity and weak interaction with Pt substrate has been established. The findings demonstrate that dehydrogenation and pyrolitic decomposition of DMAB is an efficient and easy method for obtaining a continuous almost freestanding layer mostly made of G, h‐BN with only a low percentage (<3%) of impurities (B and N‐doped G domains or C‐doped h‐BN or boron carbonitride, BCN at the boundaries) in the same 2D sheet on a metal substrate, such as Pt(111), paving the way for the advancement of next‐generation G‐like‐based electronics and novel spintronic devices.