Dimethoxydiphenylamine-substituted dispiro-oxepine derivative 2,2',7,7'-tetrakis-(N,N'-di-4-methoxyphenylamine)dispiro-[fluorene-9,4'-dithieno(3,2-c:2',3'-e]oxepine-6',9 ''-fluorene] (DDOF) has been designed and synthesized using a facile synthetic route. The novel hole transporting material (HTM) was fully characterized and tested in perovskite solar cells exhibiting a remarkable power conversion efficiency of 19.4%. More importantly, compared with spiro-OMe-TAD-based devices, DDOF shows significantly improved stability. The comparatively comprehensive solid structure study is attempted to disclose the common features of good performance HTMs. These achievements clearly demonstrated that the highly hindered DDOF can be an effective HTM for the fabrication of efficient perovskite solar cells and further enlightened the rule of new HTM's design.