The photoreduction of 4-nitrophenol to 4-aminophenol by means of protonated and exfoliated phenyl-doped carbon nitride is reported. Although carbon nitride-based materials have been recognized as efficient photocatalysts, the photoreduction of 4-nitrophenol to 4-aminophenol is not allowed because of the high recombination rate of the photogenerated electron–hole pairs. In this paper, we show the morphology effects on the photoactivity in phenyl-doped carbon nitride. Structural (TEM, XRD, Raman) and optical characterization (absorption, photoluminescence) of the protonated and exfoliated phenyl-doped carbon nitride (hereafter pePhCN) is reported. The increased photocatalytic efficiency, with respect to the bulk material, is underlined by the calculation of the kinetic constant of the photoreduction process (2.78 × 10−1 min−1 and 3.54 × 10−3 min−1) for pePhCN and bulk PhCN, respectively. Finally, the detailed mechanism of the photoreduction process of 4-nitrophenol to 4-aminophenol by modified phenyl carbon nitride is proposed.