Miscibility, rheology, and free volume properties of blends of thermotropic liquid crystalline polymers (TLCPs) (Vectra A950) and polycarbonate (PC) are studied in this work. Despite the unusual increase in T-g of the PC phase, the blends are found to be generally immiscible. Transesterification may occur during blending and be the cause of the increase of T-g of the PC phase and the partial miscibility of the blends at high TLCP concentrations. With regard to the melt rheology of these materials, according to a three-zone model, dynamic moduli of Vectra A950 show plateau- and transition-zone behavior, while PC exhibits terminal-zone behavior. The blends show only termi nal-zone behavior at low Vectra A950 contents (less than or equal to 50%) and terminal- and plateau-zone behavior at higher Vectra A950 contents. The relaxation time of Vectra A950 is much longer than PC and the blends have relaxation times greater than additivity. Both the complex and steady shear viscosities of the blends increase with the addition of Vectra A950. This is attributed to interfacial association, which retards the reorientation and alignment of the Vectra A950 phase in the molten state. The Cox-Merz rule holds true for PC but not for Vectra A950 and the blends. Free volume properties on an angstrom scale evaluated by positron annihilation lifetime spectroscopy (PALS) indicate that Vectra A950 has smaller, fewer free volume cavities than PC and the variation of free volume behavior in the blends can be explained in terms of blend miscibility. The measured densities of the blends agree well with the free volume fractions of the blends determined from PALS.