||Polyimides are already widely used in aerospace, automobile, electronics and other high-technology areas based on their excellent mix of properties. Expectations are that transparent polyimides will rapidly take hold and that their use will encompass what we now consider to be futuristic applications. The trick is to come up with the right combination of building blocks, creating a recipe where the formulations are not only developed, but are balanced and optimized. We herein report on a new class of polyimide (PI) nanohybrids based on highly fluorinated asymmetric diamines as a building block of PI backbone structure. The resulting PI nanohybrids were highly soluble in polar aprotic solvents and displayed excellent optical properties, including high transparency, low refractive index, and very small birefringence. The results provide useful information for designing molecular architectures for manufacturing high-performance flexible substrates in future display devices.