Titanium diboride thin films deposited by physical vapor deposition are typically attributed to inherent brittleness. Theoretical predictions by DFT assessing the elastic constants revealed that the formation of ternary Ti-Mo-B2±z might be a suitable approach to gain a less brittle character. In the present study, the accompanying experiments to the theoretical investigations have been conducted. Three different target compositions were used for the non-reactive growth of ternary Ti1-xMoxB2±z thin films: TiB2/MoB 95/5 mol%, TiB2/MoB 90/10 mol%, and TiB2/MoB 80/20 mol%. The binary TiB2+z system was deposited with a TiB2/C 99/1 wt.% target. In addition, direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS), were employed in order to investigate the influence of different deposition techniques – hence ionization degrees. The structural and mechanical properties of the coatings were characterized by a broad variety of methods, such as scanning electron microscopy, X-ray diffraction analysis, and nanoindentation. The chemical composition was determined by inductively coupled plasma optical emission spectrometry and elastic recoil detection analysis. To verify the suggested enhancement on the brittle behavior of Ti1-xMoxB2±z fracture characteristics such KC or KIC have been determined by cube corner indentation and in-situ micro-mechanical bending tests, respectively. Alloying of Mo leads to an increase in Ti content and a decrease in B content for both DCMS and HiPIMS deposited coatings. In contrast, the Mo content is significantly lowered while using HiPIMS. All coatings exhibit α-structured (SG191) Ti1-xMoxB2±z solid solutions. An increased hardness for both binary and ternary thin films, with a maximum value of 45 ± 1 GPa (TiB2+z) and a minimum 28 ± 0.8 GPa (~ 6 at.% Mo) can be obtained by using HiPIMS. Overall, this study highlights the influence of Mo additions on the structure-mechanical properties of TiB2±z using different growth techniques.