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 $98{sim}99%$ 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.?