Superficially porous particles are disclosed, each including a solid core and a layered porous shell. The layered porous shell includes a porous inner layer and at least one porous outer layer, a shell skeleton thickness greater than 1 nm, and constitutes from 10 vol % to 90 vol % of the plurality of superficially porous particles. The porous inner layer includes an inner layer thickness of less than 300 nm. The at least one porous outer layer includes a cumulative outer layer thickness ranging from 1 to 100 times the inner layer thickness, a predominately radial pore orientation, and an outer layer pore structure which is more organized than the inner layer pore structure. A layer-by-layer process for forming a plurality of superficially porous particles with layered structure is disclosed. A post-modification process for preparing a plurality of chromatographically enhanced superficially porous properties is also disclosed.