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In this paper, peapod-like hollow carbon nanomaterial was fabricated via an efficient one-pot hydrothermal route. The carbon–silica composite was employed as the precursor and cetyltrimethylammonium bromide (CTAB) as the morphology-controlled agent. SEM and TEM results indicated that the carbon shell and the silica core in the precursor were not closely linked but rattle-type structure. After removing the silica template, the obtained carbon product had uniform peapod-like morphology, interconnected pores and high specific surface areas (above 800.0 m²/g). We found that CTAB played an important role in the formation of the products with peapod-like morphology. The particle sizes of the hollow carbon nanospheres were readily adjusted by varying the dosage of tetraethoxysilane (TEOS) and the volume ratio of ethanol and water. Based on the experimental results, the formation mechanism of the hollow …