Microstructure evolution and mechanical properties of hypereutectoid steel with the microduplex (α+θ) structures formed by hot deformation of undercooled austenite were investigated by hot uniaxial compression tests in a Gleeble-1500 simulation test machine, and the effects of subsequent annealing and the addition of Al were analyzed. The results indicated that at the beginning of hot deformation of undercooled austenite the formation of proeutectoid cementite was retrained and only lamellar pearlite was produced. With further strain, dynamic spheroidization of pearlite took place, leading to the formation of microduplex (α+θ) structure consisting of ultrafine ferrite matrix and dispersed cementite particles. In comparison with the normal microstructure consisting of lamellar pearlite and proeutectoid cementite, the microduplex (α+θ) structure presented higher strengths with similar ductility. Subsequent annealing could make the microduplex (α+θ) structure more uniform, which demonstrated better balance between strength and ductility. The addition of Al is disadvantageous to the formation of microduplex (α+θ) structure, but can result in the further refinement. With the addition of Al, the strength of microduplex (α+θ) structure was improved and the ductility was not deteriorated markedly.