The highly-dispersed carambola-like SnO2/C composite microparticles have been fabricated through a novel electrospun approach using tetrobutylammonium bromide and paraffin liquid as functional additives in the precursor solution. The presence of carbon matrix can availably contribute for the reduced agglomeration, decreased migration, and controllable sizes of SnO2 nanocrystals. The influence of calcination temperature on the microstructures and photocatalytic properties of SnO2/C products and the relevant photocatalytic mechanism were investigated. The carambola-like SnO2/C photocatalysts showed the superior photocatalytic performance for the degradation of rhodamine B (RhB) with the high efficiency of 94.6% as the irradiation time increasing to 210 min as well as the good photocatalytic cycle stability. The preparation technology can be potentially applied for adjusting microstructures of other inorganic oxide photocatalysts in the field of water treatment. (C) 2017 Elsevier B.V. All rights reserved.