Moisture stability and brittleness are challenges for plant fiber biocomposites intended for load-bearing applications, for instance those based on an amylopectin-rich (AP) starch matrix. Core-shell amylopectin-coated cellulose nanofibers and nanocomposites are prepared to investigate effects from the distribution of AP matrix. The core-shell nanocomposites are compared with nanocomposites with more irregular amylopectin (AP) distribution. Colloidal properties (DLS), AP adsorption, nanofiber dimensions (atomic force microscopy), and nanocomposite structure (transmission electron microscopy) are analyzed. Tensile tests are performed at different moisture contents. The core-shell nanofibers result in exceptionally moisture stable, ductile, and strong nanocomposites, much superior to reference CNF/AP nanocomposites with more irregular AP distribution. The reduction in AP properties is less pronounced as the AP forms a favorable interphase around individual CNF nanofibers.