This paper uses a new kinetic modeling and simulations to analyse the effect of temperature on the polystyrene properties obtained by atom-transfer radical polymerization (ATRP). Differently from what has been traditionaly published in ATRP modeling works, it was considered "break" reactions in the mechanism aiming to reproduce the process at high temperatures. Results suggest that there is an upper limit temperature (130 degrees C), above which the polymer architecture loses the control. In addition, for the system considered in this work, the optimum operating temperature was 100 degrees C, because at this temperature polymer with very low polydispersity index is obtained, at considerable fast polymerization rate. Therefore, this present paper provides not only a tool to study ATRP processes by simulations, but also a tool for analysis and optimization, being a basis for future works dealing with this monomer and process.264313319