Flexible pressure sensors that emulate the sensation and characteristics of natural skins are of great importance in wearable medical devices, intelligent robots, and human–machine interfaces. The microstructure of the pressure-sensitive layer plays a significant role in the sensor’s overall performance. However, microstructures usually require complex and costly processes such as photolithography or chemical etching for fabrication. This paper proposes a novel approach that combines self-assembled technology to prepare a high-performance flexible capacitive pressure sensor with a microsphere-array gold electrode and a nanofiber nonwoven dielectric material. When subjected to pressure, the microsphere structures of the gold electrode deform via compressing the medium layer, leading to a significant increase in the relative area between the electrodes and a corresponding change in the thickness of the medium layer, as simulated in COMSOL simulations and experiments, which presents high sensitivity (1.807 kPa−1). The developed sensor demonstrates excellent performance in detecting signals such as slight object deformations and human finger bending.