High-performance graphene aerogels with well-developed internal structures are generally obtained by means of introducing additive materials such as carbon nanotubes, cellulose, and lignin into the aerogel network, which not only enhances the cost but also complicates the preparation process. Therefore, tailoring the internal structure of pristine graphene aerogel in a feasible way to achieve high performance is of great significance to the practical applications. Herein, a novel cysteamine/L-ascorbic acid graphene aerogel (CLGA) was fabricated by a simple one-step hydrothermal method followed by freeze-drying. Through the creative combination of the reducing agent L-ascorbic acid and cross-linking agent cysteamine, a dual-network structure was constructed by both layered physical stacking and vertical chemical cross-linking. The addition of cysteamine not only enhanced the reduction degree but also assisted the formation of more vertical connections between graphene nanosheets, resulting in more abundant pores with smaller sizes compared with graphene aerogels prepared by the traditional hydrothermal reduction method. CLGA possessed an ultra-low density of 4.2 mg/cm(3) and a high specific surface area of 397.9 m(2)/g. As expected, this dual-network structure effectively improved the absorption capacity toward a variety of oil and organic solvents, with an outstanding oil absorption capacity up to 310 g/g. Furthermore, CLGA possessed good mechanical properties and oil/water selectivity. The absorbed oil could be recovered by both continuous absorption-removal process and mechanical squeezing, making the as-prepared aerogel superior absorbent material for a variety of applications, such as selective oil absorption and water treatment.