PS microspheres emulsions with different PS diameters of 207 and 378 nm were prepared by using an emulsifier-free polymerization method. A novel secondary self-assembly method which combined the spin coating and the lifting-up method was used to prepare the close-packed PS MCC films. During the process, the PS MCC film was firstly assembled on a glass substrate by a spin coating technique. Secondly, the obtained PS MCC film was transferred on the air-water interface by immersing the PS glass substrate in water using a dip-coater. Thirdly, the floating close-packed PS MCC films on the air-water interface was transferred to a new glass substrate by using a lifting-up method. During the spin-coating and the self-assembly process, some SDS solution was added in the PS films to improve the uniformity of the PS layer. Effects of the spin-coating speeds, the SDS solution concentration and the lifting-up rates on the morphology of PS MCC films have been discussed. Scanning electron microscopy was used to observe the morphological properties of the PS colloidal crystal films. Results indicate that a relatively close-packed and large scale PS MCC films can be obtained when the spinning speed is 2000 rpm for 60 s, the SDS solution concentration is 2 wt% and the lifting-up rate is 2 mm/min. Furthermore, the polydimethylsiloxane soft mold was replicated from the-fabricated PS MCC films and was then imprinted onto the photosensitive hybrid film under UV-irradiation and thus the micro-lens arrays built in the photosensitive hybrid sol-gel film were obtained.