Summary: We discuss a family of operators which commute or anti-commute with the twisted transfer matrix of the six-vertex model at \(q\) being roots of unity, \(q^{2N} = 1\). The operators commute with the Hamiltonian of the \(XXZ\) spin chain under the twisted boundary conditions, and they are also valid for the inhomogeneous case. For the case of the anti-periodic boundary conditions, we show explicitly that the operators generate the \(sl_2\) loop algebra in the sector of the total spin operator \(S^Z\equiv N/2\bmod N\). The infinite-dimensional symmetry leads to exponentially-large spectral degeneracies, as shown for the periodic boundary conditions [T. Deguchi, K. Fabricius and B. M. McCoy J. Stat. Phys. No. 3–4, 701–736 (2001; Zbl 0990.82008 )]. Furthermore, we derive explicitly the \(sl_2\) loop algebra symmetry for the periodic \(XXZ\) spin chain with an odd number of sites in the sector \(S^Z\equiv N/2\bmod N\) when \(q\) is a primitive \(N\)th root of unity with \(N\) odd. Interestingly, inthe case of \(N = 3\), various conjectures of combinatorial formulae for the \(XXZ\) spin chain with odd sites have been given by Stroganov and other authors. We also note a connection to the spectral degeneracies of the eight-vertex model.