Functional nano-sized additives in polymers are an exciting class of hybrid materials that can tailor desirable characteristics of multiple species and realize new functionality. MXene Ti3C2 has become a candidate for self-healing hybrids. It possesses unique metallic conductivity, high aspect ratio, and broad absorption band. The self-healing properties converting electromagnetic radiation to heat depend on the absorption efficiency of Ti3C2 that varies with its concentration, geometry, size, spatial distribution, and orientation. Therefore, understanding the microstructure effect on both the optical and photothermal behaviors is important to develop a new self-healing hybrid. In addition, numerical modeling can shed light on the theoretical photothermal behaviors, which can account for many aspects of the phenomenon that cannot be experimentally obtained. In this study, the self-healing properties of two different structured Ti3C2-polyvinyl alcohol hybrid films are investigated. The characteristics of Ti3C2 and photo-induced healing behaviors are examined experimentally and numerically.