The crystallization of melts with similar composition of Portland cement liquid containing 0-5% $K_2O$ was studied by differential thermal and isothermal reaction. The devitrification of melts was occured in stages, the recognizable amount of CaO was appered at the first step, then proto-C3A was crystallized. The latter showed to occur in both cubic C3A and Ca-ferrite crystallization. Batches lost remarkable amounts of $K_2O$ as a result of volatilization during melting and the solubility of $K_2O$ in the melts was unstable.