advanced functional templates, such as porous supraparticles and complex crystal superstructures, due to their facile surface functionalization and tunable colloidal assembly. [1][2][3][4][5][6] Films fabricated from latex colloids with a unique core-shell morphology is a novel class of nanoparticlepolymer composites that synergistically integrate the versatility of nanoparticles (core) with the processability and diversity of the corona polymers (shell). [5,7] Two techniques, that is, seeded free-radical emulsion polymerization and controlled radical emulsion polymerization of amphiphilic block copolymers (commonly a macro chain-transfer agent), have proven effective in devising multifunctional coreshell latex colloids. [7][8][9] In the above-mentioned techniques, the seed of the latex colloid or the hydrophobic core that is derived from the polymerization-induced self-assembly in aqueous dispersion functions as an interfacial modulator to direct hydrophobic polymer growth on the core surface or in the core, respectively. [10,11] Compared with controlled radical emulsion polymerization, seeded emulsion polymerization offers more possibilities to vary the constituents of the core (e.g., polyesters, polyolefins, polyvinyl acetate, acrylics, polysaccharides, silica) and distinct shell geometries, such as raspberry-and dumbbell-like features, Fabricating bio-latex colloids with core-shell nanostructure is an effective method for obtaining films with enhanced mechanical characteristics. Nanosized lignin is rising as a class of sustainable nanomaterials that can be incorporated into latex colloids. Fundamental knowledge of the correlation between surface chemistry of lignin nanoparticles (LNPs) and integration efficiency in latex colloids and from it thermally processed latex films are scarce. Here, an approach to integrate self-assembled nanospheres of allylated lignin as the surface-activated cores in a seeded free-radical emulsion copolymerization of butyl acrylate and methyl methacrylate is proposed. The interfacial-modulating function on allylated LNPs regulates the emulsion polymerization and it successfully produces a multi-energy dissipative latex film structure containing a lignin-dominated core (16% dry weight basis). At an optimized allyl-terminated surface functionality of 1.04 mmol g −1 , the LNPs-integrated latex film exhibits extremely high toughness value above 57.7 MJ m −3 . With multiple morphological and microstructural characterizations, the well-ordered packing of latex colloids under the nanoconfinement of LNPs in the latex films is revealed. It is concluded that the surface chemistry metrics of colloidal cores in terms of the abundance of polymerization-modulating anchors and their accessibility have a delicate control over the structural evolution of core-shell latex colloids.