The bond dissociation–recombination behavior of dynamically crosslinked networks provides a fundamental physical mechanism underlying the ordered alignment of nanomaterials. This study employs dynamic covalent hydrogels as a model system to systematically elucidate the precise regulation mechanism of cellulose nanocrystal (CNCs) alignment under uniaxial stretching. Results revealed that the rapid recombination of reversible bonds facilitates the effective dissipation of localized stress and serves as “molecular-level bearings”, which guide the coordinated rotation and long-range alignment of CNCs along the stretching direction. Besides, under optimized conditions, the resulting composite material exhibits a birefringence of 0.00461 and an orientation index of 0.90754, indicating pronounced optical anisotropy. Through mechanistic understanding, we established a comprehensive processing–structure–property relationship by correlating key parameters (precursor composition, stretching conditions, and geometric dimensions) with the resulting microscopic orientation and macroscopic optical performance. This investigation establishes a foundation for identifying the critical processing window required for developing high-performance, low-cost, and sustainable photonic materials.