The use of bio-based nanoscaled cellulose for the construction of novel functional materials has progressed rapidly over the past years. In comparison to most of studies starting with the hydrophilic nanoscaled cellulose, surface-stearoylated cellulose nanoparticles (SS-CNPs) are used in this report for the construction of multifunctional, responsive films. SS-CNPs with an average size of 115 +/- 0.5 nm are obtained after the surface-modification of cellulose under heterogeneous conditions. Crystalline cellulose core is present within SS-CNPs according to solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. SS-CNPs show excellent dispersibility in nonpolar solvents and form temperature-responsive organogels in tetrahydrofuran (THF) at low temperature or after long time storage at room temperature. Moreover, transparent and self-standing films of SS-CNPs from their THF-suspension show solvent-responsive surface wettability and responsive shape-memory property. SS-CNPs can also be used for the fabrication of nanocomposite films together with nonpolar compounds, such as (2-stearoylaminoethyl) rhodamine B. Thus, these novel SS-CNPs derived from sustainable cellulose fibers are promising candidates for the construction of novel functional materials.