<p>The development of organic afterglow materials with high environmental stability and multi-mode luminescence remains a significant challenge in luminescent anti-counterfeiting. In this work, an organic luminescent molecule was encapsulated within polyacrylamide microspheres and embedded in a gold nanorod-doped, ferric ion-crosslinked hydrogel exhibiting upper critical solution temperature behavior. The obtained composites exhibited fluorescence, thermally activated delayed fluorescence, and phosphorescence. Through the application of extrusion or uniaxial stretching, the orientation of the gold nanorods was modulated, enabling polarization-dependent luminescence through transverse surface plasmon resonance absorption. At 300% uniaxial strain, the polarized fluorescence intensity difference at 520 nm reached 0.29. Furthermore, ultraviolet irradiation was employed to locally disrupt the orientation of the gold nanorods, resulting in depolarization within the irradiated regions. These areas displayed non-polarized fluorescence, while the non-irradiated regions retained both emission and fluorescence polarization characteristics. Localized imprinting was employed to modulate material thickness, thereby controlling the density of gold nanorods. Thinner regions exhibited weaker transverse localized surface plasmon resonance absorption, while thicker regions showed stronger absorption, enabling the coexistence of blue–green fluorescence and polarization patterns. Local humidification effectively reduced phosphorescence intensity, enhancing the material’s environmental responsiveness. The composite demonstrated excellent reversibility over multiple stretching–self-healing cycles and pattern-switching processes, highlighting its strong potential for multidimensional optical encryption and intelligent anti-counterfeiting applications.</p>