Iridates have been providing a fertile ground for studying emergent phases of matter that arise from the delicate interplay of various fundamental interactions with approximate energy scale. Among these highly focused quantum materials, the perovskite Sr2IrO4, which belongs to the Ruddlesden–Popper series, stands out and has been intensively addressed in the last decade, since it hosts a novel Jeff = 1/2 state that is a profound manifestation of strong spin–orbit coupling. Moreover, the Jeff = 1/2 state represents a rare example of iridates that is better understood both theoretically and experimentally. Here, Sr2IrO4 is taken as an example to review the recent advances of the Jeff = 1/2 state in two aspects: materials fundamentals and functionality potentials. In the fundamentals part, the basic issues for the layered canted antiferromagnetic order of the Jeff = 1/2 magnetic moments in Sr2IrO4 are illustrated, and then the progress of the antiferromagnetic order modulation through diverse routes is highlighted. Subsequently, for the functionality potentials, fascinating properties such as atomic‐scale giant magnetoresistance, anisotropic magnetoresistance, and nonvolatile memory, are addressed. To conclude, prospective remarks and an outlook are given.