<p>Chiral luminescent materials with multiple functions are critically significant for multimodal anti-counterfeiting systems and information encryption, but the design strategy still faces challenges. Herein, the (R-)/(S-)-QPPTZ with aggregate conformational isomerism is ingeniously designed and synthesized, exhibiting diverse photophysical properties in poly(methyl methacrylate) matrix. Quasi-equatorial (eq) conformation with highly twisted configuration exhibits enhanced intramolecular charge transfer, which leads to shorter excitation but longer emission wavelengths. The bent configuration of the quasi-axial (ax) conformation confers inverse excitation and emission behaviors. Meanwhile, the transition characters of excited states are also manipulated by the conformational configuration, in which the intersystem crossing (ISC) is effectively facilitated, assisting in the generation of triplet excitons and enabling photoactivated phosphorescence. Multiple functionalities, including excitation-dependent emission, photoactivated room-temperature phosphorescence (RTP), and circularly polarized luminescence (CPL), are simultaneously realized within the single-molecule-based system. Finally, a four-dimensional (4-D) anti-counterfeiting label is successfully demonstrated. This work not only advances the understanding of influences of molecular conformation on the molecular properties but also presents a promising strategy for multimodal anti-counterfeiting.</p>