Size is one of the central issues in nanoscience. The practical meaning of the term "sub-nanometric material (SNM)" requires two aspects: (1) its size should be at the atomic level; (2) it shows unique (size-related) properties compared to its nano-counterparts with larger sizes. Here, SNMs in the form of wires (SNWs) and the unique properties arising from their special size are reviewed. First, their polymer-like behavior, including rheological behavior and self-assembly, is dicussed. Their origins may stem from the special size and the ligands around the wire. Even a slight increase in diameter would risk the polymer-like behavior. Meanwhile, the ligands on SNWs are proportional to the inorganic entity at this scale. Consequently, surface ligands should have a profound impact on the properties, like catalysis, self-assembly, optics, etc. To reveal more potential applications, their applications in energy conversion are comprehensively reviewed. To some extent, characterization can greatly influence the way things are observed. Thus, some appropriate characterization techniques are briefly introduced. Finally, another emerging part of SNWs (atomic chain material) is briefly introduced. It is hoped that this review can provide new insights to this special scale.