A three-dimensional organic aerogel nano-network with high structural stability and strength was obtained by physically bonding polyacrylonitrile (PAN) nanofibers into a resorcinol-formaldehyde (RF) nano-network. The PAN nanofibers were produced by the electrospinning of PAN solution. The PAN fibers were then oxidized, to produce oxidized polyacrylonitrile (O-PAN) nanofibers. The two fibers were added separately into the RF nano-network to generate a new hybrid RF aerogel. The RF aggregates were co-assembled onto the surfaces of the electrospun PAN and O-PAN fibers during the gelation process. Which increased the RF structural stiffness, strength, and resilience. Further, graphene oxide (GO) sheets were added to the mixtures as a crosslinker between the fibers. With the GO sheets presence, the number of the RF aggregates on the surface of the fibers increased by an order of magnitude because of the hydrogen bonds formed between the amino groups on the fibers and the functional groups on the GO. The final RF aerogels with O-PAN nanofibers and GO sheets had double the strength and resilience and three times the stiffness compared to the traditional RF aerogels while maintaining their light weight characteristics and low thermal conductivity of 30 mW/m.K.