Ultra-high-purity (UHP) electronic-grade octamethylcyclotetrasiloxane (D4) is the key precursor of lowdielectricconstant (low-k) SiCOH films to manufacture integrated circuits (IC), meeting the stringentrequirements of the rapidly developing semiconductor industry. Commonly, metallic impurities in D4were removed by multiple unit operations of adsorption, filtration, and distillation, which could reducethe concentration of a single metallic impurity below 1 ppb. However, D4 with higher purity is requiredby semiconductor production due to an increase in transistor density. Herein, a novel method based onthe integrated simultaneous distillation–extraction (SDE) was developed for manufacturing UHPelectronic-grade D4. The lab and pilot scale experiments showed that the purity of water and D4 has apositive correlation. Based on the experimental data, a double-column process, consisting of azeotropic/extractive distillation column and precision distillation column with UNIQUAC method, was establishedto access the feasibility of scaling up the SDE process. According to the simulation results, D4with the purity > 99.999 wt.% and total metallic impurities (TMI) content below 1 ppb could be obtainedusing ultra-pure water.