Mechanical coating process was applied to form 89 %-hydrolyzed poly vinyl alcohol (PVA) onto boron carbide (B_4C) 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 B_4C/PVA was about 50 nm. The core/shell structured B_4C/PVA was formed by dry milling. However, the hydrolyzed PVA of 98sim99% with high glass transition temperature (T_g) was rarely coated on the powder. The T_g of polymer materials was one of keys for guest polymer coating on to the host powder by solvent free milling.