A series of polyimide (PI) nanocomposite films with various surface-modified colloidal calcium carbonate (SCaCO3) contents were prepared and their physical properties were investigated to understand their possible use as polymer substrates. The morphology, thermal stability, residual stress behavior, moisture barrier and optical properties of nanocomposite films were investigated as a function of the SCaCO3 content and were found to be strongly dependent upon the chemical and morphological structures. With the addition of up to 0.5 wt% SCaCO3 in the PI matrix, resultant nanocomposite films exhibit not only enhanced thermal properties, but also minimized residual stress and excellent optical properties, simultaneously. With increasing SCaCO3 content, the water vapor transmission rate (WVTR) is greatly decreased from 630.76 to 484.22 g/m2/day. The residual stress was in the range of 26.0 to 12.1 MPa and is highly dependent on both temperature variation and SCaCO3 content. Although the residual stress becomes lower at 0.5 wt% SCaCO3 content, it increases at relatively high SCaCO3 loadings due to inadequate dispersion of the SCaCO3 and low interfacial interactions between the polymer and filler surfaces. Therefore, further studies are needed to maximize the performance of nanocomposite films by enhancing the compatibility of the polymer matrix and fillers.