Over twenty million tons of pineapples have been produced annually worldwide, but their waste is mostly discarded or burnt after harvesting. In this work, the high-value added aerogels from the pineapple leaf waste are developed for the first time by using polyvinyl alcohol (PVA) cross-linkers and a cost-effective freeze drying process. The pineapple fibre (PF) aerogels have highly porous structures with the porosities of 96.98–98.85%, ultra-low densities of 0.013–0.033 g/cm³, and hydrophobicity with water contact angles of approximately 140°, after a surface modification with methyltrimethoxysilane (MTMS). The effects of PF concentrations (0.5–2.0 wt.%) on oil and organic solvent adsorption are investigated comprehensively. Experimental results indicate that the hydrophobic PF aerogels can adsorb motor oil up to 37.9 g/g, approximately two times greater than commercial polypropylene and polyurethane sorbents. The pseudo-second order model can provide a good fit for the oild adsorption kinetics of the developed aerogels.