Dynamic contact angle measurements and X-ray photoelectron spectroscopy (XPS) were used to investigate the surface compositions and surface rearrangement of poly(imide-siloxane) with various molecular weights and contents of amine-terminated poly(dimethyl siloxane) (ATPDMS). Four different water contact angles were measured to study the poly(imide-siloxane) surface: the initial advancing angle, the equilibrium advancing angle, the initial receding angle, and the equilibrium receding angle. Poly(imide-siloxane) with 2350 and 4300 g/mol of ATPDMS showed higher initial and equilibrium advancing contact angles than those of poly(imide-siloxane) with 433 g/mol of ATPDMS. Since the mobility of ATPDMS segments depended on the chain length of ATPDMS, the molecular weight of ATPDMS determined the surface composition of poly(imide-siloxane), the rate of surface rearrangement, and the contact angle hysteresis. Poly(imide-siloxane)s with 2850 and 4300 g/mol of ATPDMS were mostly covered with ATPDMS even if just 1 wt% of ATPDMS was incorporated, while poly(imide-siloxane) with 433 g/mol of ATPDMS was mostly covered with polyimide segments and partially with ATPDMS. The rate of surface rearrangement and the contact angle hysteresis decreased with the increasing molecular weight as well as content of ATPDMS. The actual ATPDMS-enriched layer thickness was also investigated by XPS. The actual thickness of the ATPDMS-enriched layer was about 15 nm for 2850 g/mol and 4300 g/mol of ATPDMS-modified poly(imide-siloxane) and about 7.5 nm for 433 g/mol of ATPDMS-modified poly(imide-siloxane).