Investigation of the potential use of nanofibers to reinforce composites has gained significance in many applications. In this article, the nanofiber mats of poly(acrylic acid) (PAA) and styrene–butadiene–styrene (SBS) triblock copolymer with composites structure were interweaved by double needle electrospinning process. The multiple nanofiber mats were added to conventional water-swellable rubber (WSR). Improved mechanical and physical properties of WSR were obtained. Enhancement of the swellability of WSR + PAA/SBS nanofiber mats was derived from the PAA constituent absorbing water from the surface into the bulk and introducing random internal water channels between discontinuous superabsorbent polymers. The role of SBS nanofibers in the composite of WSR + PAA/SBS nanofiber mats was more related to the mechanical properties, where the breaking force of the composite increased to twice that of the conventional WSR. Interestingly, after immersion of the WSR + PAA/SBS nanofiber mats in water for 1 week, there was only a slight decrease in their mechanical properties of less than 5% compared to the dry state. The mechanisms and effects of the nanofiber mats in enhancing the mechanical and water swelling properties of WSR are also discussed.