Although crystalline nanocellulose (CNCs) can be extracted from different resources, the employed pretreatments, which disrupt the inter- and intramolecular physical interactions, depend on the biomass sources. This study aims to valorize Aloe Vera (AV) rinds into cellulose and crystalline nanocellulose (CNC) employing two approaches during hydrolysis: sulfuric acid (CNC_SA) and citric acid (CNC_CA) after 30, 60, and 90 min of reaction. The effects of pretreatments and hydrolysis time on the functional groups and hydrogen bonding in biomass are discussed. Crystalline structure (polymorph type), crystallinity, thermal stability, morphology, particle size, and metal presence are also analyzed. A transformation from type I into II polymorph was achieved, where the intermolecular interactions governing cellulose were increased in CNC_SA and were almost maintained in CNC_CA. Properties based on the structure, thermal properties, particle size, and metal presence indicate that the CNC_SA30 and CNC_CA90 samples displayed potential application as reinforcement agents for other types of polymers having no more melting points of 160 and 220 °C, respectively.