The production of cellulose nanofibrils (CNFs) continues to receive considerable attention because of their desirable material characteristics for a variety of consumer applications. There are, however, challenges that remain in transitioning CNFs from research to widespread adoption in the industrial sectors, including production cost and material performance. This Review covers CNFs produced from nonconventional fibrillation methods as a potential alternative solution. Pretreating biomass by biological, chemical, mechanical, or physical means can render plant feedstocks more facile for processing and thus lower energy requirements to produce CNFs. CNFs from nonconventional fibrillation methods have been investigated for various applications, including films, composites, aerogels, and Pickering emulsifiers. Continued research is needed to develop protocols to standardize the characterization (e.g., degree of fibrillation) of the lignocellulosic fibrillation processes and resulting CNF products to make them more attractive to the industry for specific product applications.