Demolding is a necessary process in polymer micro molding, which requires energy for fracture of the bonds between the mold and the polymer. This often leads to structural defects due to an inappropriate combination of process parameters, including demolding temperature, embossing force or injection pressure, separation rate, and separation mode. In this article, we focus on the theoretical analysis and experimental optimization of the process parameters for polymer micro‐part demolding from a zirconium (Zr)‐based bulk metallic glass mold. We developed a theoretical model to predict the demolding work, in which we considered the effects of sidewall friction combined with deformation and adhesion. We also optimized the parameters for the demolding process based on the Taguchi method. The experimental results showed that the embossing force and the separation mode had significant effects on the demolding work of hot embossing. We determined the optimum process parameters and found that with these parameters the demolding work could be decreased to 10.36 mJ in this case. POLYM. ENG. SCI., 59:2202–2210, 2019. © 2019 Society of Plastics Engineers