Graphitic carbon nitride (g-C₃N₄) hybridized with a small number of multi-walled carbon nanotubes (CNT) was synthesized using cyanamide as precursor. The optimal CNT content is found to be ∼0.2 wt% in the composite, which displays a 2.4-fold enhancement in photocatalytic water splitting over pure g-C₃N₄. Characterizations by a series of joint techniques including Raman spectra, UV/vis diffuse reflectance spectra, steady and time-resolved fluorescence emission spectra, and photocurrent responses were carried out, aiming to reveal the determinative factor for the improved visible-light response. Our results indicate that the increased photoactivity originates from the enhanced charge-transfer effect due to the intimate interactions between g-C₃N₄ and conjugated CNT. The presence of CNT in the hybrids is beneficial for improving electron–hole separation on the excited g-C₃N₄ by prolonging the lifetimes of charge carriers and improving the population distribution of short-lived and long-lived charge carriers.