Gigantic polytypes of sp3-bonded boron nitride prepared by plasma-laser hybridized CVDSp3-bopnded iono-covalent bonded crystals such as SiC are known to show polytypes, which originate from the variety of stacking modes of densely packed layers of atoms along c-axis. Here we report the Boron Nitride (BN) polytypes with extraordinary large unit cell prepared by plasma-laser synchronous CVD from diborane and ammonia. In addition to usual plasma-assisted CVD, we irradiate the growing film surface with ArF excimer laser at 193 nm. The typical pulsed-laser frequency was 10 Hz. The laser irradiation proved to induce a phase-transformation through which diamond-like denser phases of BN are produced during the CVD process.