The reactivity of open-shell titanium(III) complexes in organometallic catalysis is associated with many open questions, in particular regarding the electronic structure of catalytic intermediates and transition states. The unpaired electron density in principle allows for radical-type reactivity, while at the same time empty d orbitals allow more traditional cis-coordination insertion pathways. In this paper we investigated the (Cp*)2TiIII-catalyzed cross-dimerization of aliphatic and aromatic acetylenes, focusing on the reactivity of two different aliphatic acetylenes with a series of different aromatic acetylenes. The applied aliphatic acetylenes 1a (4-methylpent-1-yne) and 1b (N,N-dimethyl-N-propargylamine) have the same size but different electron-accepting abilities. The better π-accepting substrate 1b shows a higher reactivity and selectivity than substrate 1a in the studied cross-dimerization reactions. Stronger π back-donation from the titanium-localized SOMO to the substrate thus seems to be a reasonable explanation for the improved selectivity of substrate 1b. DFT calculations indeed suggest a stronger binding of substrate 1b as compared to that of 1a in the selectivity-determining steps of the reaction, thus leading to faster insertions and higher selectivities with substrate 1b.