The alkali-metal clinopyroxene NaTi(3+)Si2O6, one of the rare compounds with trivalent titanium, was synthesized at high temperature/high pressure and subsequently investigated by single-crystal X-ray diffraction methods between 298 and 100 K. One main difference between the high- and the low-temperature form is the sudden appearance of two different Ti(3+)-Ti3+ interatomic distances within the infinite chain of the TiO6 octahedra just below 197 K. This change can be seen as direct evidence for the formation of Ti-Ti singlet pairs in the low-temperature phase. Mean Ti-O bond lengths smoothly decrease with decreasing temperature and the phase transition is associated with a slight jump in the Ti-O bond length. The break in symmetry, however, causes distinct variations, especially with respect to the two Ti-O(apex) bond lengths, but also with respect to the four Ti-O bonds in the equatorial plane of the octahedron. The TiO6 octahedron appears to be stretched in the chain direction with a slightly larger elongation in the P1; low-temperature phase compared with the C2/c high-temperature phase. Polyhedral distortion parameters such as bond-length distortion and octahedral angle variance suggest the TiO6 octahedron in P1; to be closer to the geometry of an ideal octahedron than in C2/c. Mean Na-O bond lengths decrease with decreasing temperature and the variations in individual Na-O bond lengths are the result of variations in the geometry of the octahedral site. The tetrahedral site acts as a rigid unit, which does not show pronounced changes upon cooling and through the phase transitions. There are neither large changes in bond lengths and angles nor in polyhedral distortion parameters, for the tetrahedral site, when they are plotted. In contrast with the C2/c-->P2(1)/c phase transition, found especially in LiMSi2O6 clinopyroxenes, no very large variations are found for the tetrahedral bridging angle. Thus, it is concluded that the main factor inducing the phase transition and controlling the structural variations is the M1 octahedral site.