Nonconventional luminogens with high quantum yield (QY) possess very potential applications in various fields. However, the preparation of such luminogens remains a great challenge. Herein, the first example of piperazine-containing hyperbranched polysiloxane exhibiting blue and green fluorescence is reported under the irradiation of different excitation wavelength and a high QY of 20.9%. The density functional theory (DFT) calculations and experimental results revealed that the through-space conjugation (TSC) within the clusters of N and O atoms is produced via the induction of multiple intermolecular hydrogen bonds and flexible SiO units, which is accountable for the fluorescence. Meanwhile, the introduction of the rigid piperazine units not only rigidifies the conformation, but also enhances the TSC. In addition, the fluorescence of both P1 and P2 shows concentration-, excitation-, and solvent-dependent emission, especially exhibits significant pH-dependent emission and obtains an ultrahigh QY of 82.6% at pH 5. The synthetic luminogens show excellent applications in fluorescence detection for Fe³⁺ and Co²⁺, information encryption, and fluorescent film. This study provides a novel strategy to rationally design high-efficiency nonconventional luminogens.