Carbon nanofibers (CNF) are widely used as active agents for electrodes in Li-ion secondary battery cells, supercapacitors, and fuel cells. Nanoscale coatings on CNF electrodes can increase the output and lifespan of battery devices. Atomic layer deposition (ALD) can control the coating thickness at the nanoscale regardless of the shape, suitable for coating CNFs. However, because the CNF surface comprises stable C–C bonds, initiating homogeneous nuclear formation is difficult because of the lack of initial nucleation sites. This study introduces uniform nucleation site formation on CNF surfaces to promote a uniform SnO2 layer. We pretreat the CNF surface by introducing H2O or Al2O3 (trimethylaluminum + H2O) before the SnO2 ALD process to form active sites on the CNF surface. Transmission electron microscopy and energy-dispersive spectroscopy both identify the SnO2 layer morphology on the CNF. The Al2O3-pretreated sample shows a uniform SnO2 layer, while island-type SnOx layers grow sparsely on the H2Opretreated or untreated CNF.