The increasing demand for sustainable textile recycling has driven the development of effective methods to separate and recover valuable materials from fabric waste. Elastane, synthetic polymer that has found extensive application in the textile industry on account of its elasticity and durability, presents considerable environmental challenges in the recycling process. Consequently, the development of effective methods for elastane degradation is of paramount importance in order to mitigate its environmental impact. The employment of conventional disposal techniques, including incineration and landfil, has been identified as a significant contributor to environmental pollution and the degradation of valuable materials. This underscores the necessity for the development of alternative recycling processes. Dimethylformamide (DMF) and dimethylacetamide (DMAc) are two organic solvents that are frequently employed in the chemical processing of textiles for the removal of elastane. However, it is evident that both solvents have notable environmental toxicity, health risks and regulatory constraints. This study evaluated the potential of biobased organic solvents for the direct elastane solubilisation of elastane. The solvents under scrutiny included cyrene (CYR), γ-valerolactone (GVL), and tetrahydrofurfuryl alcohol (THFA) in the presence and in the absence of an organic catalyst, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN). In addition, a case study was conducted using a polyester/elastane fabric in order to assess the practical application of these solvents. The findings indicated that GVL-DBN and THFA, when used in the absence and with DBN, respectively, exhibited efficacy in elastane dissolution through the exhaustion method over a duration of one hour at temperature of 80 °C. The dissolution of elastane was evaluated through mechanical testing by determining the breaking strength, elongation and Young’s modulus. Moreover, the physicochemical analysis was performed by Fourier transform infrared spectroscopic method with attenuated total reflectance (ATR-FTIR) and thermogravimetric analysis (TGA). This research contributes to the advancement of circular economy practices in the textile industry by introducing a novel approach for elastane dissolution using safer and more eco-friendly DBN, thus offering a viable pathway for the recycling of elastane-containing materials and the replacement of hazardous DMF and THFA.