The structure and dielectric properties of BaAl(2−2x)(Zn0.5Ti0.5)2xO4 ceramics were investigated. Single-phase solid solutions in space group P63 (No. 173) were confirmed when 0% ≤ x ≤ 1.6%. [Zn0.5/Ti0.5]3+ averagely occupied four symmetrically inequivalent Al sites, and Al1/(Zn,Ti)–O, Al2/(Zn,Ti)–O and Al3/(Zn,Ti)–O bond lengths increased with increased x. Two dielectric anomalous peaks existed, the first peak referred to second-order ferroelectric transition. Stability was significantly improved by moving the first dielectric abnormal peak from 123 °C to −22 °C due to the lower atomic shift amplitude Δz of B cations along the polar axis. The co-doping of Zn2+ and Ti4+ played a decisive role in realizing an ultrabroad temperature range (−100 °C–700 °C) of stability (−27 ppm/°C ≤ TCC ≤ +10 ppm/°C), which met the conditions of C0G or NP0 multilayer ceramic capacitors (±30 ppm/°C). Superior insulating properties were performed by high resistivity of > 1014 Ω cm.