The catalytic dehydration of a bio-based fatty alcohol was performed using Al2O3 prepared by solvothermal synthesis for selective production of long-chain linear-alpha-olefins (LAO). The effect of the synthesis temperature of alumina precursors on the dehydration of 1-octadecanol (C18H38O) was examined based on the textural properties and Lewis acid-base properties of the catalysts. Amorphous alumina synthesized at 325 °C showed the highest surface area (233.07 m2/g) and total pore volume (1.237 cm3/g) among the catalysts and the best dehydration results: 93% conversion, 62% selectivity of 1-octadecene (C18H36), and 89% LAO purity. This was attributed to the increased Al/O ratio and atomic concentration of surface O in alumina, which were important factors in the catalytic dehydration of 1-octadecanol through the synergistic catalysis of acid-base pairs. The produced bio-based LAO can be key intermediates for synthesis of oxo alcohols and poly-alpha-olefins, as alternatives to petroleum-based LAO to achieve carbon neutrality in chemical industry.