In the present work, significantly various structures connected by Al-O/OH/acetate-Al bonds were synthesized in a versatile sol-gel route. The various bond systems result in several three-dimensional (e.g., fibrous, highly porous, and compact) macrostructures. The shared acetate and OH ions provide the fibrous character; the shared OH ions and oxygen-bridges between octahedral Al(III) ions assist in the formation of a porous network; and the oxygen-bridges between differently (octa-, tetra-, and pentahedrally) coordinated Al(III) ions characterize the compact structures. The newly developed synthesis route is a fast and low-energy consumption sol-gel technique. This method applies only two starting materials and does not adopt any basic agent or catalyst. The synthesis is fast because it does not require any time-consuming peptization; a 3-D network forms directly from the initial solution. The low energy consumption arises from the low temperature of reactions (80 °C) and heat treatment (400-600 °C).