With the improvements of large-scale parallel replication and automation for hot embossing machines, hot embossing has become not only popular in laboratories but also possible and attractive in industry. Most difficulties in polymer micro-molding are caused by the demolding of molds rather than the filling of them. Due to the lack of accurate analysis tools and simulation tools for demolding, it is difficult to improve the process or give design rules for the molds, which could harm the further applications of hot embossing. This paper gives our studies of the demolding process using LIGA mold inserts. The demolding forces mainly consist of thermal shrinkage stress and adhesive forces. First, a finite elements method (FEM) is applied to analyze thermal stress caused by the shrinkage differences between the mold and polymer using ABAQUS/Standard, and a thermal stress barrier is proposed as an auxiliary structure to protect against the converging stress at the bottom corner of microstructures. Then, regarding the adhesion and friction forces, the nanotribology of PMMA is studied by AFM with nickel and PTFE-coated Si₃N₄ tips. And based on the measurements, the adhesion and friction forces in a demolding cycle are also simulated by FEM using ABAQUS/Standard. At last Ni-PTFE is recommended as the mold material for achieving a lower surface energy and lower friction force. This work proposes several methods that can optimize the demolding process and introduces some good suggestions for mold tool design.