The uranium reserve in seawater is enormous, but its concentration is extremely low and plenty of interfering ions exist; therefore, it is a great challenge to extract uranium from seawater with high efficiency and high selectivity. In this work, a symbiotic aerogel fiber (i.e., PAO@ANF) based on polyamidoxime (PAO) and aramid nanofiber (ANF) is designed and fabricated via in-situ gelation of ANF with PAO in dimethyl sulfoxide and subsequent freeze-drying of the corresponding fibrous gel precursor. The resulting flexible porous aerogel fiber possesses high specific surface area (up to 165 m2·g−1), excellent hydrophilicity and high tensile strength (up to 4.56 MPa) as determined by BET, contact angle, and stress-strain measurements. The batch adsorption experiments indicate that the PAO@ANF aerogel fibers possess a maximal adsorption capacity of uranium up to 262.5 mg·g−1, and the absorption process is better fitted by the pseudo-second-order kinetics model and Langmuir isotherm model, indicating an adsorption mechanism of the monolayer chemical adsorption. Moreover, the PAO@ANF aerogel fibers exhibit selective adsorption to uranium in the presence of coexisting ions, and they could well maintain good adsorption ability and integrated porous architecture after five cycles of adsorption–desorption process. It would be expected that the symbiotic aerogel fiber could be produced on a large scale and would find promising application in uranium ion extraction from seawater.