Ti layer inserted in the TiN gate electrode effectively scavenges the oxygen in the low‐k interfacial SiO2 of the metal–ferroelectric–insulator–semiconductor (MFIS) capacitors with the ferroelectric Al‐doped HfO2 (HAO) thin film. The scavenging effect increases remanent polarization (Pr) and reduces coercive voltage (Vc) and capacitance equivalent thickness (CET) of the HAO films, particularly when the MFIS capacitor is annealed at 800 °C. Additionally, frequency dispersion of capacitance characteristics and interface trap density (Dit) calculations reveal that actively‐triggered oxygen‐scavenging effects also reduce defect or trap‐induced degradation. The Ti‐inserted MFIS structure exhibits fatigue‐free endurance and relatively low leakage current characteristics as compared to a structure without the Ti scavenging layer in high annealing temperature conditions required for crystallization of the HAO ferroelectric films.