Since the famous Swedish chemist Scheele described molybdenum blue for the first time in 1778, polyoxometalate (POM) chemistry has made significant progress in its more than 200-year history. Compared with the POM chemistry of Mo, W and V, significant improvement of polyoxotantalates (POTas) occurred mainly during the last few years. In this paper, complexes with different structures, including isopolyoxotantalates (IPOTas), organic-inorganic hybrid POTas, Ta/W mixed POMs and heteropolyoxotantalates (HPOTas) with their derivatives, are reviewed, aiming at providing some useful guidance for further exploration and discovery of more exciting POTas with innovative architectures and excellent performances. Herein, we highlight and discuss the structural features of POTas according to various structural types. In addition, the synthesis strategies and related applications, especially in photocatalysis, are reviewed.