In the present paper, a series of novel conjugated polymers, poly［(silylene)acetylene silanes］ with different structure, were prepared, and the luminescence performance of the poly［(silylene)acetylene silanes］ with different substituents were investigated by the fluorescence and UV absorption spectroscopic approaches. The effect of different substituents and the number of acetylene in the main chain on the luminescence was discussed in depth. The result showed that these polymers have moderate absorbance in the range from 219 to 260 nm. The red shift was showed for the maximum absorbance wavelength following the increase in the number of the acetylene and the degree of the conjugation in the main chain. There was insignificant difference in the maximum absorbance wavelength of the polymers with dimethy and diphenyl. In short, the influence of the substituents is insignificant. However, the remarkable effect was induced by the conjugated structure in the main chain. The conjugated polymers with different structure in the main chain have moderate fluorescence and emission quantum yields. The authors studied the influence of the polymers’ structure on the luminescence performance. As a result, the influence of the substituents is insignificant for emission spectra. The influence of the conjugated groups in the main chain of the polymers is remarkable. The maximum emission wavelength of the polymers showed an evident shift to red range with the enhancement of the conjugated extent. These polymers had good thermal properties for the special structures. So they have potential applications for emission materials with good thermal stability.