Mechanical coating process was applied to form 89 %-hydrolyzed poly vinyl alcohol (PVA) onto boron carbide (B4C) nanopowder using one step high energy ball mill method. The polymer layer coated on the surface of B4C was changed to glass-like phase. The average particle size of core/shell structured B4C/PVA was about 50 nm. The core/shell structured B4C/PVA was formed by dry milling. However, the hydrolyzed PVA of 98~99% with high glass transition temperature (Tg) was rarely coated on the powder. The Tg of polymer materials was one of keys for guest polymer coating on to the host powder by solvent free milling.