In this work, we present a straightforward method to attach a globular dendrimer at the reducing end of cellulose nanocrystals obtained from tunicates (t-CNC). We investigated the first four generations of poly(amidoamine) dendrimers (PAMAMs G0 to G3) to obtain hybrid t-CNCs. The aggregation behavior of hybrid t-CNCs was studied by dynamic light scattering (DLS) and scanning transmission electron microscopy (STEM); and interactions of these asymmetric nanoparticles with gold surface were elucidated using quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR). Hybrid t-CNCs formed hairy layers onto gold surface combining the properties of rigid rod-like nanocrystals with globular and flexible PAMAM dendrimers. Moreover, the presence of amino groups provided pH-responsive properties to hybrid t-CNCs, and QCM-D results revealed reversible swelling/deswelling behavior. Thereby, we achieved to synthesize tree-shaped functional bio-based materials that adsorbed on gold and formed pH-responsive hairy surfaces.