Metal–organic frameworks (MOFs) are widely used as supports for single-atom catalysts (SACs) owing to their high specific surface area, porosity, and ordered metal–ligand structure. Their activity can be increased by increasing the number of electrochemically accessible active sites via the formation of atomically dispersed metal catalysts (M–Nx) that coordinate with nitrogen atoms on the MOF. Herein, we introduce the relationship between the size of the MOF as a starting material and the catalytic activity for the oxygen reduction reaction in alkaline media. The morphology and features of the MOFs are critically dependent on their size. Remarkably, cage-like MOFs below 33 nm are converted into collapsed structures and are connected between each MOF, even carbon fiber- or tube-like features, after carbonization. SACs derived from medium-sized MOFs exhibit excellent activity and are comparable to commercial Pt/C catalysts owing to their porous structure. Therefore, we believed that controlling the size of MOFs containing active atoms is an effective method of modulating the morphological properties of the support and even the number of active sites that are closely related to the activity.