Ni-supported catalyst is a viable system to convert methane and carbon dioxide into syngas through methane dry reforming, with the main drawbacks of its fast deactivation being sintering and coking. Here, we developed methods to engineer a TiOx overlayer on Ni/TiO2 catalysts to shield the catalyst against sintering and coking while preserving the Ni accessibility and, thus, conversion. These methods involved altering TiO2crystal phases, pretreatment, and reaction conditions in the reforming stage. Through characterization, testing, and operando spectroscopy, we found that the TiOx overlayer with incomplete Ni coverage maintained a balanced conversion and stability by quenching the sintering and coking. Conversely, thick or nonexistent overlayers led to lower conversions or faster deactivation. The formation of TiOx overlayer increased the CO2activation capacity and oxygen mobility and protected Ni from sintering by its shield function. At the same time, the reaction pathways remained unchanged despite the TiOx overlayer with different morphologies.