The effect of Si incorporation on the crystallization process and crystal structure of Te-free Sb-rich GeSb was investigated in this study. Si concentrations were controlled to 0, 5.1, 9.3, and 12.8 at.% by controlling the sputtering power of the GeSb alloy target (20:80 at.% for Ge:Sb) and Si target. After film deposition, the crystallization process and crystal structure were investigated. Crystallization temperature increased from 320 to 400 A degrees C and the overall crystallinity was decreased with increasing Si concentration. These were analyzed by sheet resistance measurements after thermal annealing and optical contrast measurements by optical static testing. Glass transition temperatures were calculated and increased from 240 to 285 A degrees C with increasing Si concentration. Considering the proportional relation between the glass transition temperature and crystallization temperature, it is thought that more energy is required for crystallization with increased Si concentration. A study of the crystallization process kinetics was conducted by applying the Johnson-Mehl-Avrami model to the optical static test results, which were carried out under a pseudo-isothermal process. The Avrami coefficient was 4.10 and decreased to 3.18 when the crystallization was generated with increased Si concentration from 0 to 12.8 at.%. Therefore, crystallization speed was thought to decrease with increased Si concentration. Based on the results of crystal structure analysis by XRD and HRTEM, the crystal structure of our Sb-rich GeSb PCM was revealed to be a typical Sb structure, i.e., an A7 hexagonal structure with lattice parameters of a = 4.26 and c = 11.45 . No crystal phase of Ge or Si was observed and no evidence of the structure change in Sb crystals due to Ge or Si incorporation was observed.