Cellulose micro- and nanofibers (CNFs) are commonly regarded as “greener” than petro-based materials. The high energy input that their production still demands, along with the use of chemicals or heat in some pretreatments, asks for a critical view. This paper attempts a life cycle assessment of CNFs produced from bleached hardwood kraft pulp via three different pre-treatments before mechanical homogenization. First, a fully mechanical route, based on a Valley beating pre-treatment. Second, an enzymatic route, based on endoglucanases and requiring certain temperature (~50 °C). Third, a TEMPO-mediated oxidation route, considering not only the impact of the chemical treatment itself but also the production of TEMPO from ammonia and acetone. The main output of the study is that both, mechanical and TEMPO-mediated oxidation routes, present lower impacts than the enzymatic pre-treatment. Although the mechanical route presents slightly milder contributions to climate change, acidification, eutrophication, and other indicators, saying that TEMPO-mediated oxidation is environmentally unfeasible should be put under question. After all, and despite being disregarded in most assessment publications up to date, it is the only well-known way to selectively oxidize primary hydroxyl groups and thus producing kinds of CNFs that are unthinkable by other ways.