As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C13H26O3, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl2, FeCl3, CuBr2, and FeBr3 on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (Ea) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMRad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr2. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.