In this study, facile construction engineering of Pr6O11@C with efficient photocatalytic activity was established. Taking advantage of the flocculation of Pr3+ in the base medium, acid red 14 (AR14) was flocculated together with Pr(OH)3 precipitate, in which Pr(OH)3 and AR14 mixed highly uniformly. Calcinated at high temperature in N2, a novel Pr6O11@C was successfully synthesized. The resulting materials were characterized by XRD, SEM, FT-IR, Raman, and XPS techniques. The results show that the cubic Pr6O11@C with Fm3m space group, similar to that of Pr6O11, was obtained. From the results of the photodegradation of AR14, it is found that the photocatalytic efficiency of Pr6O11@C is higher than that of pure Pr6O11 due to the formation of abundant carbon bonds and oxygen vacancies. Compared with pure Pr6O11 and other carbon-based composites, the acid resistance of Pr6O11@C is greatly improved due to the highly uniform dispersion of Pr6O11 and C, which lays a solid foundation for the practical application of Pr6O11@C. Moreover, the role of NH3·H2O and NaOH used as precipitants for the photocatalytic efficiency of Pr6O11 was investigated in detail.