[en] The synthesis of polynitrogen compounds is of great importance due to their potential as high-energy-density materials (HEDM), but because of the intrinsic instability of these compounds, their synthesis and stabilization is a fundamental challenge. Polymeric nitrogen units which may be stabilized in compounds with metals at high pressure are now restricted to non-branched chains with an average N-N bond order of 1.25, limiting their HEDM performances. Herein, we demonstrate the synthesis of a novel polynitrogen compound TaN${}_5$ via a direct reaction between tantalum and nitrogen in a diamond anvil cell at circa 100 GPa. TaN${}_5$ is the first example of a material containing branched all-single-bonded nitrogen chains [N${}_5$${}^{5-<!--\; ???\; -->}$]${}_{\mathrm{\infty <!--\; ???\; -->}}$. Apart from that we discover two novel Ta-N compounds: TaN${}_4$ with finite N${}_4$${}^{4-<!--\; ???\; -->}$ chains and the incommensurately modulated compound TaN${}_{2-<!--\; ???\; -->x}$, which is recoverable at ambient conditions. (© 2021 Wiley-VCH GmbH)