Optical encryption technologies are widely used in information security, whereas the technology with one single optical secret key can be easily cracked. Here, a triple encryption is reported, which hides patterned information in excitation‐dependent allochroic materials with long afterglow, enhancing the security level. The allochroic materials are based on a uniaxial co‐assembly structure of cellulose nanocrystals (CNCs) and silica. The assembled CNCs present blue emission with quantum yield of 19.8% under 367 nm UV radiation. The blue emission is maintained in the inverse structure when CNCs are calcinated and converted to carbon dots (CDs). The inverse uniaxial‐assembly structure improves the CD emission by 6.7 times. The assembly structure can even improve the phosphorescence of CDs, leading to excellent excitation‐dependent allochroic properties. Specifically, the materials maintain a cyan long afterglow luminescence at 480 nm after removing 365 nm UV light, whose lifetime is 0.492 s. Changing the excitation wavelength to 254 nm, a UV emission at 343 nm can be obtained, alongside a blue long afterglow luminescence of 420 nm, whose lifetime is 1.574 s. Combining with blue afterglow materials, optical encryption labels are prepared, which hide different patterned information in three scenarios: natural light, UV light, and afterglow luminescence.