In this work, the novel natural rubber latex (NRL) mixing was approached. The mixing process was carried out by using n-hexane as the dispersed phase of silica aerogel which acted as thermal insulation filler prior to NRL mixing. The silica aerogel/NR composites were prepared with different silica aerogel contents of 20, 40, 60, 80, and 100 parts per hundred rubber (phr). The morphology of the 40 phr composite showed the NR macropore formation with silica aerogel intercalated layers. The optimal content of silica aerogels and n-hexane were the key to obtaining the NR macropore. The thermal insulation performance of silica aerogel/NR composites was investigated because of their porous structures. The thermal conductivity of the composites were lower than that of the neat NR sheet and decreased from 0.081 to 0.055 W m−1·K−1 with increasing silica aerogel content. The lower densities of the composites than that of the NR sheet were revealed noticeably. In addition, the silica aerogel/NR composites exhibited a higher heat retardant ability than that of the NR sheet, and the comparable glass transition temperatures (Tg) of the composites and the neat NR indicated the maintained flexibility at ambient temperature or higher, which can benefit various temperature applications. The overall results demonstrated that the silica aerogel/NR composites from the novel NRL mixing preparation could be a promising technique to develop the porous materials and be utilised as thermal insulation products and building constructions.