The rational design of lightweight, broad‐band, and high‐performance microwave absorbers is urgently required for addressing electromagnetic pollution issue. Metal single atoms (M–SAs) absorbers receive considerable interest in the field of microwave absorption due to the unique electronic structures of M–SAs. However, the simultaneous engineering of the morphology and electronic structure of M–SAs based absorbers remains challenging. Herein, a template‐assisted method is utilized to fabricate isolated Co–SAs on N‐doped hollow carbon spheres (NHCS@Co–SAs) for high‐performance microwave absorption. The combination of atomically dispersed Co sites and hollow supports endows NHCS@Co–SAs with excellent microwave absorption properties. Typically, at an ultralow filler content of 8 wt%, the minimum reflection loss and effective absorption bandwidth of the NHCS@Co–SAs are up to −44.96 dB and 5.25 GHz, respectively, while the absorbing thickness is only 2 mm. Theoretical calculations and experimental results indicate that the impedance matching characteristic and dielectric loss of the NHCSs can be tuned via the introduction of M–SAs, which are responsible for the excellent microwave absorption properties of NHCS@Co–SAs. This work provides an atomic‐level insight into the relationship between the electronic states of absorbers and their microwave absorption properties for developing advanced microwave absorbers.