Young's moduli of cellulose nanofibril (CNF)-poly(allylamine hydrochloride) (PAH) multilayered thin films were measured using strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) and the quantitative nanomechanical mapping technique (PF-QNM). To establish the relationship between structure and mechanical properties, three types of films with various architectures were built using the layer-by-layer method by changing the ionic strength of the dipping solution. Both methods demonstrate that the architecture of a film has a strong impact on its mechanical properties even though the film has similar cellulose content, emphasizing the role of the architecture. Films with lower porosity (Φair = 0.34) and a more intricate network display the highest Young's moduli (9.3 GPa), whereas others with higher and similar porosity (Φair = 0.46-0.48) present lower Young's moduli (4.0-5.0 GPa). PF-QNM measurements indicate a reverse ranking that is probably indicative of the surface composition of the films.