Cellulose nanofibers (NF) were extracted from kapok fibers using TEMPO oxidation, followed by a combination of mechanical grinding and ultrasonic processing. The TEMPO-mediated oxidation significantly impacted the mechanical disintegration behavior of the kapok fibers, resulting in a high NF yield of 98%. This strategy not only improved the fibrillation efficiency but also reduced overall energy consumption during NF preparation. An ultralight and highly porous NF-based aerogel was successfully prepared using a simple ice-templating technique. It had a low density in the range of 3.5–11.2 mg cm−3, high compressional strength (160 kPa), and excellent thermal insulation performance (0.024 W m−1 K−1). After silane modification, the aerogel displayed an ultralow density of 7.9 mg cm−3, good hydrophobicity with a water contact angle of 128°, and excellent mechanical compressibility with a high recovery of 92% at 50% strain. Benefiting from the silene support structure, it showed a high oil absorptive capacity (up to 71.4 g/g for vacuum pump oil) and a remarkable oil recovery efficiency of 93% after being reused for 10 cycles. These results demonstrate that our strategy endows nanocellulose-based aerogels with rapid shape recovery and high liquid absorption capabilities.