UiO-66-NH is a metal-organic framework (MOF) with open metal sites, making it a promising candidate for adsorption and catalysis. However, the powdery texture of MOFs and the use of toxic solvents during synthesis limit their application. A novel solution to this issue is to create a layered porous composite by encasing the MOF within a flexible and structurally robust aerogel substrate using safe, eco-friendly, and green solvents such as ethanol. The fibrous MOF aerogels, characterized by a desirable macroscopic shape of cylindrical block and hierarchical porosity, were synthesized by two approaches: in situ growth of amine-functionalized UiO-66-NH crystals on a TEMPO-oxidized cellulose nanofiber (TOCNF) and ex situ crosslinking of UiO-66-NH crystals onto a TOCNF network to form UiO-66-NH/TOCNF. The incorporation of MOF into the cellulose nanofibrils via the in situ method reduces their aggregation potential, alters the nucleation/growth balance to produce smaller MOF crystals, and enhances mechanical flexibility, as evidenced by SEM images. The three adsorbents, including UiO-66-NH, ex situ UiO-66-NH/TOCNF, and in situ UiO-66-NH/TOCNF, were synthesized and used in this study. The effects of pH, time, temperature, and initial concentration were studied. A maximum adsorption capacity (Qmax) of 549.45 mg/g for Congo Red (CR) and 171.23 mg/g for Orange II (ORII) was observed at pH 6, using 10 mg of in situ UiO-66-NH/TOCNF at 40 °C with a contact time of 75 min for CR and 2 h for ORII. The adsorption of both dyes primarily occurs through monolayer chemisorption on the in situ UiO-66-NH/TOCNF. The main removal mechanisms were hydrogen bonding and surface complexation. The noteworthy adsorption capacity of in situ UiO-66-NH/TOCNF coupled with environment-friendly fabrication techniques indicates its potential applications on a large scale in real wastewater systems.