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Because of its less toxicity and electronic structure analogous to that of lead, tin halide perovskite (THP) is currently one of the most favorable candidates as an active layer for optoelectronic and electric devices such as solar cells, photodiodes, and field‐effect transistors (FETs). Promising photovoltaics and FETs performances have been recently demonstrated because of their desirable electrical and optical properties. Nevertheless, THP's easy oxidation from Sn2+ to Sn4+, easy formation of tin vacancy, uncontrollable film morphology and crystallinity, and interface instability severely impede its widespread application. This review paper aims to provide a basic understanding of THP as a semiconductor by highlighting the physical structure, energy band structure, electrical properties, and doping mechanisms. Additionally, the key chemical instability issues of THPs are discussed, which are identified as the potential bottleneck for further device development. Based on the understanding of the THPs properties, the key recent progress of THP‐based solar cells and FETs is briefly discussed. To conclude, current challenges and perspective opportunities are highlighted.

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Herein, the synthesis of the novel acceptordonor-acceptor( A-D-A)-structured small molecule Si-PO-2CN based on dithienosilole (DTS)a sb uilding block flanked by electron-rich phenoxazine (POZ) units, which are terminated with dicyanovinylene, is presented. Si-PO-2CN showed unique electrochemical and photophysical properties and has been successfully employed in perovskite solar cells (PSCs) as well as in bulk heterojunction organic solarc ells (OSCs).T he PSCs fabricated with dopant-free Si-PO-2CNa s hole-transport material (HTM) exhibited ap owerc onversion efficiency (PCE) of 14.1 %( active area = 1.02 cm 2 ). Additionally,aPCE of 5.6 %h as been achievedf or OSCs, which em-ployedS i-PO-2CN as p-type donorm aterialw hen blended with a[ 6,6]-phenyl C71b utyric acid methyl ester (PC 71 BM) acceptor. The versatilea pplicationo fS i-PO-2CN provides a pathway for furtheri mplementationo fD TS-based building blocksi ns olar cells for designing new molecules.

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