Herein, the synthesis of the novel acceptor–donor–acceptor (A–D–A)-structured small molecule Si-PO-2CN based on dithienosilole (DTS) as building 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 solar cells (OSCs). The PSCs fabricated with dopant-free Si-PO-2CN as hole-transport material (HTM) exhibited a power conversion efficiency (PCE) of 14.1 % (active area=1.02 cm2). Additionally, a PCE of 5.6 % has been achieved for OSCs, which employed Si-PO-2CN as p-type donor material when blended with a [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) acceptor. The versatile application of Si-PO-2CN provides a pathway for further implementation of DTS-based building blocks in solar cells for designing new molecules.