Neutral Ti[CN](n) complexes have been investigated with quantum chemistry techniques. According to our theoretical predictions, these complexes are shown to prefer isocyanide arrangements. Therefore, these compounds are good candidates to be the first polyisocyanides to be characterized. The theoretical calculations predict Ti(NC)(4), a methane-like tetrahedral structure with four isocyanide ligands, as the most stable neutral complex. The fact that the isocyanide ligand is a better pi-donor than the cyanide one seems to be the key factor for the preference for isocyanides in neutral titanium complexes.