Bur-like microspheres and microwires of CuS/pyridine composites were synthesized by a solvothermal method. The spheres or wires composed of a large number of nanoflakes with thickness of 10-20 nm and length of hundreds nanometers. Sub-nanostructures can be observed in the nanoflakes by the high-resolution transmission electron microscopy (HR-TEM) patterns. A large blue shift of band-gap absorption of CuS was observed in the composites, which was attributed to quantum confinement effect (QCE) induced by the sub-nanostructures. Pure Cu9S5 microspheres and CuS/Cu9S5 microwires were obtained by extracting the inorganic-organic composites with ethylene glycol. Possible formation mechanisms were discussed.