Catalyst selection is very crucial for controlled growth of single-walled carbon nanotubes (SWNTs). Here we introduce a well-designed Fesingle bondTisingle bondO solid solution for SWNT growth with a high preference to large chiral angles. The Fesingle bondTisingle bondO catalyst was prepared by combining Ti layer deposition onto premade Fe nanoparticles with subsequent high-temperature air calcination, which favours the formation of a homogeneous Fesingle bondTisingle bondO solid solution. Using CO as the carbon feedstock, chemical vapour deposition growth of SWNTs at 800 °C was demonstrated on the Fesingle bondTisingle bondO catalyst. Nanobeam electron diffraction characterization on a number of individual SWNTs revealed that more than 94% of SWNTs have chiral angles larger than 15°. In situ environmental transmission electron microscopy study was carried out to reveal the catalyst dynamics upon reduction. Our results identify that the phase segregation through reducing Fesingle bondTisingle bondO catalyst leads to the formation of TiOx-supported small Fe nanoparticles for SWNT growth. The strong metal-support interactions induced by partial reduction of TiOx support promote the wettability of Fe nanoparticle, accounting for the preferential growth of large-chiral-angle SWNTs. This work opens a new avenue for chiral angle selective growth of SWNTs.