Aluminum oxynitride (AlON) exhibits excellent mechanical properties and good optical transparency in the ultraviolet to near-infrared range and can be used in military and civilian fields. However, the troublesome molding of AlON, especially for complex shapes, limits its promotion and application. Therefore, transparent AlON ceramics with complex morphologies were prepared for the first time by a novel spontaneous coagulation casting (SCC) and pressureless sintering method. In this study, we report a simple carbothermal reduction and nitridation (CRN) method for synthesizing high-purity AlON powder, which is especially suitable for wet casting without anti-hydration treatment. The dispersion and gelation behavior of AlON slurries by isobutene maleic anhydride copolymer (Isobam104) and tetramethylammonium hydroxide (TMAH) were extensively investigated. With the addition of 0.9 wt% Isobam104 and 15 mL/L TMAH, the AlON slurries can achieve a solids loading of up to 45 vol% with the lowest viscosity (460.4 mPa·s-10 r/min) and the AlON green body is free of cracks and deformation during drying and demolding processes. Finally, the AlON green bodies with square and polygonal irregular morphologies were fabricated via a simple SCC method. High transparent AlON ceramics of a maximum transmittance up to 77.3% at 2000 nm and 72.2% at 632 nm were obtained by pressureless sintered at 2000 °C for 6 h. The SCC method has great potential in preparing ceramics with controllable shapes.