Olive tree pruning (OTP) is one of the most abundant sources of biomass waste in the Mediterranean basin. This is especially relevant in southern Spain where olive oil production represents a large part of the economy. Olive tree prunings are mostly either burned or are spread in olive orchards as an organic amendment, or used for heat generation on a domestic scale. However, the lignocellulosic composition of OTP makes it a potential source of biopolymers, thus providing an excellent economic alternative for the olive oil sector. In this work, pretreated OTP fibers were subjected to an optimized alkaline treatment followed by a single‐step bleaching reaction with H2O2. Afterwards, the cellulose pulp was transformed chemically to obtain cellulose acetate. Noncellulosic components were removed effectively from OTP, thus obtaining a pulp highly purified in cellulose with 71% crystallinity and 355 °C maximum degradation temperature. Nevertheless, a very large amount of cellulose (ca. 50%) was eliminated throughout the process, especially during acid pretreatment, which was responsible for 38% solubilization. A similar level of acetylation and degree of substitution was obtained by using acetylation times in the range of 1 to 6 h. No large differences were observed in the infrared spectra and X‐ray diffractograms of the synthesized acetates. However, their thermal stability varied significantly with reaction time, evolving from a multistep degradation pattern to a single and sharp peak between 300 and 400 °C with increasing time. Thermogravimetric curves revealed that at least 5 h (preferably 6 h) were needed to obtain cellulose acetate from OTP with adequate thermal stability for further processing.