Endowing a single material with various types of luminescence, that is, exhibiting a simultaneous optical response to different stimuli, is vital in various fields. A photoluminescence (PL)‐ and mechanoluminescence (ML)‐based multifunctional sensing platform is built by combining heterojunctioned ZnS/CaZnOS:Mn²⁺ mechano‐photonic materials using a 3D‐printing technique and fiber spinning. ML‐active particles are embedded in micrometer‐sized cellulose fibers for flexible optical devices capable of emitting light driven by mechanical force. Individually modified 3D‐printed hard units that exhibit intense ML in response to mechanical deformation, such as impact and friction, are also fabricated. Importantly, they also allow low‐pressure sensing up to ≈100 bar, a range previously inaccessible by any other optical sensing technique. Moreover, the developed optical manometer based on the PL of the materials demonstrates a superior high‐pressure sensitivity of ≈6.20 nm GPa⁻¹. Using this sensing platform, four modes of temperature detection can be achieved: excitation‐band spectral shifts, emission‐band spectral shifts, bandwidth broadening, and lifetime shortening. This work supports the possibility of mass production of ML‐active mechanical and optoelectronic parts integrated with scientific and industrial tools and apparatus.

The optically active dopant distribution in a Tm3+–Yb3+ doped silica based glass ceramic sample has been investigated. A systematic analysis of the upconversion fluorescence of the Tm3+–Yb3+ codoped glass and glass ceramic has been performed at room temperature. Tm3+ and Yb3+ single doped glass and glass ceramics have also been included in the study. Upon infrared excitation at 790 nm into the H43 level of the Tm3+ ions a blue upconversion emission is observed, which is drastically increased in the Yb3+ codoped samples. A rate equation model confirmed the energy transfer upconversion mechanism. Based on these results, the temporal dynamic curves of the levels involved in the upconversion process, H43, F5/22, and G41 were interpreted in the glass ceramic samples. The contribution of the optically active Tm3+ and Yb3+ ions in the crystalline and in the vitreous phase of the glass ceramic was distinguished and the ratio of Tm3+ ions in the crystalline phase could be quantified for the 1 mol % Tm3+–2.5 mol % Yb3+ glass ceramic. A surprising result was obtained for that concentration: the main contribution to the upconversion emission of the glass ceramic is due to Tm3+–Yb3+ ions in the vitreous phase.