Accurately determining the morphology and hence the true surface areas of catalytic nanoparticles remains challenging. For many chemically synthesised nanoparticle suspensions conventional BET surface area measurements are often not feasible due to the large quantities of material required. For platinum, a paradigmatic catalyst, this issue is further complicated by the propensity of this metal to form porous aggregate structures comprised of smaller (ca. 2-5 nm) crystallites as opposed to continuous solid structures. This dendritic/porous particulate morphology leads to a large but poorly defined 'active' surface which is difficult to measure accurately. Here we compare, single nanoparticle electrochemistry with three dimensional (3D) electron tomography and quantitative 2D high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) analysis to yield insights into the porosity and chemically accessible surface area of a 30 nm diameter commercial Pt nanoparticle catalyst. Good quantitative agreement is found between 2D and 3D STEM-based measurements of the particle morphology, density and size distribution. Both 3D STEM tomography and single nanoparticle electrochemical measurements allow quantification of the surface area but the electrocatalytic surface area is found to be 2.8× larger than is measured in STEM; indicating the importance of the atomic scale roughness and structure (<2 nm) in contributing to the total catalytic surface area of the nanomaterial.