The single-component white-light-emitting materials play an essential role in the next-generation solid-state lighting technology. Herein, linear gold(I) complex TPPGPA with conglobate trimer configuration trigged by aurophilic interactions in crystalline state was prepared to emit dual phosphorescent white-light emission, which also exhibited multi-stimuli responsive luminescent properties including thermochromism and mechanochromism. Specifically, the molecular packing mode and aurophilic interactions regulation were subtly taken as a functional relationship of the experimental correlation with emission. The results showed that the regulated aurophilic interactions and restriction of molecular motion were determined to be the precipitating factor and as a function of the wavelength and intensity, which is significant for the design guide about intelligent stimuli-responsive white-light emissive luminescent materials. Furthermore, their application in temperature-responsive white-light illumination was successfully demonstrated.