Spent coffee grounds (SCG) are the waste byproducts of coffee brewing. While SCG can be valorized to produce functional biopolymers due to their valuable structural components, the lignocellulosic structure of SCG is resistant to degradation because of the tightly bound lignin. Therefore, a pretreatment step is required before pulping with peracetic acid (PAA), an eco-friendlier alternative to traditional pulping methods, to facilitate the extraction of these desired cellulosic materials. Formic acid:acetic acid:deionized water (FA:AA:W = 30:50:20) or 60% (v/v) ethanol pretreatments were applied to SCG to compare the characteristics of the resulting cellulosic materials after PAA pulping. Lignocellulose analysis showed that the lignin content (7.06%) of ethanol pretreated SCG was significantly lower (p < 0.05), and the cellulose content (29.52%) was significantly higher (p < 0.05) than the untreated SCG (15.50% and 11.50%, respectively), indicating that an adequate amount of lignin was removed to obtain the cellulosic materials after the pretreatment process. Morphological and structural changes in the lignin and hemicellulose were observed in all the pretreated SCG, which further confirmed that these components were degraded with pretreatments and pulping. Ethanol pretreated SCG showed the most optimal results based on the greatest lignin decrease seen from its lignocellulose composition, appearance, and structure. This study exemplified a conversion process to extract cellulosic materials from SCG more efficiently to utilize for cellulose-based products and verify its potential to be valorized as a waste byproduct. PRACTICAL APPLICATION: Coffee companies can provide the spent coffee grounds (SCG) they produce to develop cellulose-based materials to make biodegradable packaging products rather than throwing them out or burning them. Using SCG for producing cellulose-based materials can help promote sustainability and reduce food waste worldwide. SCG can be utilized as an alternative source based on their abundance and desired biopolymeric properties, providing innovative solutions to industries and increasing consumer awareness of this cause.