Spin-coating one polymer solution on another spin-cast polymer film is believed to result in unfavorable interfacial mixing. Here, we show some results to demonstrate that some interesting properties will be obtained in such mixed bilayer films formed by sequential spin-coating. Poly(9-vinylcarbazole) and poly(9,9-dioctylfluorene-2,7-diyl) were chosen as the first and second polymer layers, respectively. By varying the initial thickness of the first layer, some interesting variations were observed. The spectroscopic features of beta-phase polyfluorene were utilized to reflect the variations at the complicated interface. Morphologies were also presented to illustrate that the variations of spectroscopic features were accompanied with some interesting morphological changes. On the basis of these results, a schematic model was proposed to gain insight into the mixed interface formed by sequential spin-coating. Polymer light-emitting devices based on such films were also investigated.