β-1,3-Glucans are ubiquitously observed in various biological systems with diverse physio-ecological functions, yet their underlying assembly mechanism and multiscale complexation in vitro remains poorly understood. Here, we provide for the first-time evidence of unidentified β-1,3-glucan supramolecular complexation into intricate hierarchical architectures over several length scales. We mediated these unique assemblies using a recombinantly produced β-1,3-glucan phosphorylase (Ta1,3BGP) by fine-tuning solution conditions during particle nucleation and growth. We report a synthesis of interconnected parallel hexagonal lamellae composed of 8 nm thick sheets of highly expanded paracrystals. The architecture consists of β-1,3-glucan triple-helices with considerable inter-intra hydrogen bonding within, as well as in between adjacent triple-helices. The results extend our understanding of β-1,3-glucan molecular organization and shed light on different aspects of the crystallization processes of biomolecules into structures unseen by nature. The presented versatile synthesis yields new materials for diverse medical and industrial applications.