PLA nanofibers are of great interest in tissue engineering due to their biocompatibility and morphology; moreover, their physical properties can be tailored for long-lasting applications. One of the common and efficient methods to improve polymer properties and slow down their degradation is sol-gel covalent crosslinking. However, this method usually results in the formation of gels or films, which undervalues the advantages of nanofibers. Here, we describe a dual process sol-gel/electrospinning to improve the mechanical properties and stabilize the degradation of PLA scaffolds. For this purpose, we synthesized star-shaped PLAs and functionalized them with triethoxysilylpropyl groups (StarPLA-PTES) to covalently react during nanofibers formation. To achieve this, we evaluated the use of (1) a polymer diluent and (2) different molecular weights of StarPLA on electrospinnability, StarPLA-PTES condensation time and crosslinking efficiency. Our results show that the diluent allowed the fiber formation and reduced the condensation time, while the addition of low-molecular-weight StarPLA-PTES improved the crosslinking degree, resulting in stable matrices even after 6 months of degradation. Additionally, these materials showed biocompatibility and allowed the proliferation of fibroblasts. Overall, these results open the door to the fabrication of scaffolds with enhanced stability and prospective long-term applications.