Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics, including water-solubility, biocompatibility and environmental friendliness, and have shown potential applications in diverse fields. As an indispensable branch of nonconventional luminescent materials, polysiloxanes which consist of electron-rich auxochromic groups, have exhibited outstanding photophysical properties due to the unique silicon atom. The flexible Si-O bonds benefit the aggregation, and the empty 3d orbitals of Si atom can generate coordination bonds like N → Si and O → Si, altering the electron delocalization of the material and improving the luminescent purity. Herein, we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives. With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions, the role of Si atoms played in the nonconventional luminophores is highlighted. This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing, biomedicine, lighting devices, etc.