AbstractThe capacity to withstand challenges posed by complex environments is crucial for developing advanced high‐performance protective materials with mechanically adjustable nature. By constructing long‐range hierarchical network of shear‐stiffening gel‐carbon nanotube‐cellulose nanofiber (SCC) embedded within epoxy resin (ER), this work engineers a nacre‐inspired variable‐stiffness SCC‐ER composite (SCCE). Lightweight SCC scaffold attenuates falling impact force from 2.23 to 0.46 kN, and reaches 60 °C within 20 s under 1 sun exposure. Additionally, owing to the rigid ER matrix, SCCE exhibits 4.03 GPa elastic modulus, outperforming numerous conventional engineering materials in puncture resistance. Specific energy absorption of nacre‐mimetic SCCE presents 1.91 MJ m−3 while that of random structural SCCE is only 0.50 MJ m−3. More importantly, SCCE features representative photothermal‐induced reversible rigidity whose storage modulus varies from 9.85 MPa at 30 °C to 11.61 kPa at 116 °C under light stimulation. It also presents shape‐programmability, capable of adhering complex structural surfaces for protection. Eventually, SCCE‐based semi‐active adjustable protectors are constructed that leverage contactless photothermal effect to modulate rigidity. 5 mm‐thick smart SCCE‐protectors resist 163.93 m s−1 ballistic impact while 15‐mm commercial kneepads are penetrated at lower speed of 136.98 m s−1. This bio‐inspired semi‐active strategy proposes a promising avenue for enhancing personal protective equipment.