<p>The thermal stability of Pt particles is crucial for volatile organic compounds (VOCs) catalytic oxidation. Herein, a coordinated unsaturated aluminum (CUA) with abundant pentacoordinate Al³⁺ sites (Al^3 + _penta) stabilizing platinum catalyst was synthesized by the solution combustion method followed the incipient wetness impregnation method for VOCs degradation. The Pt particles exhibited well dispersion after 800&#xa0;°C calcination, comparied with Pt loaded on commercial γ-Al₂O₃, detectd by SEM and TEM. The heat-resistant sintering was related to the anchoring of Pt by Al^3 + _penta proved by ²⁷Al NMR. The turnover frequency (TOF) of Pt/CUA for toluene oxidation was as high as 2.58&#xa0;h^-1 under 60,000 ml^-1 g^-1 h^-1 and 5% water steam, which is about 2 times higher than that of Pt/γ-Al₂O₃. Furthermore, after 800&#xa0;°C calcination, the TOF of Pt/CUA-800 was increased to 4.57&#xa0;h^-1 in comparison with 0.4&#xa0;h^-1 for Pt/γ-Al₂O₃-800. The excellent catalytic performance was maybe due to the Pt dispersion, low temperature reducibility and high surface chemsorbed oxygen species characterized by pulsed CO chemisorption, H₂-TPR and XPS. Anchorage effect of Al^3 + _penta on Pt metal was shown to be an effective strategy for the enhancement of VOCs composition.</p> Graphical Abstract <p></p>