Acetylation of cellulose fiber extracted by methylbenzene/ethanol (2/1), sodium chlorite solution, and sodium hydroxide from raw wheat straw (RWS) was studied to examine its potential as an oil-spill adsorbent. Wheat straw cellulosic sorbent was produced by using acetic anhydride as an acetylating reagent and N-bromosuccinimide (NBS) as a catalyst. Effects of the volume ratio of acetic anhydride (from 6.25% to 57.5%), catalyst concentration (from 10 to 60 mM NBS), reaction temperature (from 50 to 120 °C), and reaction time (from 0.5 to 3 h) on oil-sorption properties were evaluated. The best oil absorbencies for diesel fuel, diesel oil slick, corn oil, and corn oil slick treatments were 24.21 ± 0.76, 22.39 ± 0.77, 25.61 ± 2.13, and 24.73 ± 1.19 g/g, respectively. Chemical composition and morphologic structure of RWS before and after acetylation were investigated and compared. Oil-absorption capacity, oil-retention ability, recyclability, and selectivity of RWS, pretreated wheat straw, and acetylated wheat straw were also discussed. The acetylated wheat straw demonstrated good potential for the utilization of agricultural residues as natural sorbents in oil cleanup.