Hypothesis: Although many synthetic pathways allow to fine-tune the morphology of dendritic mesoporous silica nanoparticles (DMSNs), the control of their particle size and mesopore diameter remains a challenge. Our study focuses on either increasing the mean particle size or adjusting the pore size distribution, changing only one parameter (particle or pore size) at a time. The dependence of key morphological features (porosity; pore shape and pore dimensions) on radial distance from the particle center has been investigated in detail.& nbsp; Experiments: Three-dimensional reconstructions of the particles obtained by scanning transmission electron microscopy (STEM) tomography were adapted as geometrical models for the quantification of intraparticle morphologies by radial porosity and chord length distribution analyses. Structural properties of the different synthesized DMSNs have been complementary characterized using TEM, SEM, nitrogen physisorption, and dynamic light scattering.& nbsp; Findings: The successful independent tuning of particle and pore sizes of the DMSNs could be confirmed by conventional analysis methods. Unique morphological features, which influence the uptake and release of guest molecules in biomedical applications, were uncovered from analyzing the STEM tomography-based reconstructions. It includes the quantification of structural hierarchy, identification of intrawall openings and pores, as well as the distinction of pore shapes (conical vs. cylindrical).& nbsp; (c) 2021 Elsevier Inc. All rights reserved. Hypothesis: Although many synthetic pathways allow to fine-tune the morphology of dendritic mesoporous silica nanoparticles (DMSNs), the control of their particle size and mesopore diameter remains a challenge. Our study focuses on either increasing the mean particle size or adjusting the pore size distribution, changing only one parameter (particle or pore size) at a time. The dependence of key morphological features (porosity; pore shape and pore dimensions) on radial distance from the particle center has been investigated in detail. Experiments: Three-dimensional reconstructions of the particles obtained by scanning transmission electron microscopy (STEM) tomography were adapted as geometrical models for the quantification of intraparticle morphologies by radial porosity and chord length distribution analyses. Structural properties of the different synthesized DMSNs have been complementary characterized using TEM, SEM, nitrogen physisorption, and dynamic light scattering. Findings: The successful independent tuning of particle and pore sizes of the DMSNs could be confirmed by conventional analysis methods. Unique morphological features, which influence the uptake and release of guest molecules in biomedical applications, were uncovered from analyzing the STEM tomography-based reconstructions. It includes the quantification of structural hierarchy, identification of intrawall openings and pores, as well as the distinction of pore shapes (conical vs. cylindrical).