Large‐scale and high‐quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large‐sized and single‐crystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large‐sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h‐BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in‐depth growth dynamics and kinetics. Finally, relevant issues for industrial‐scale mass production of 2D single crystals are discussed and a promising future is expected.