Dye effluent has attracted considerable attention from worldwide researchers due to its harm and toxicity in recent years; as a result, the treatment for dye has become one of the focuses in the environmental field. Adsorption has been widely applied in water treatment owing to its various advantages. However, the adsorption behaviors of the new materials, such as the 2D black phosphorus (BP), for pollution were urgently revealed and improved. In this work, BP, black phosphorene (BPR), and sulfonated BPR (BPRS) were prepared by the vapor phase deposition method, liquid-phase exfoliating method, and modification with sulfonation, respectively. The three BP-based materials were characterized and used as adsorbents for the removal of methylene blue (MB) in water. The results showed that the specific surface areas (SSAs) of BP, BPR, and BPRS were only 6.78, 6.92, and 7.72 m2·g−1, respectively. However, the maximum adsorption capacities of BP, BPR, and BPRS for MB could reach up to 84.03, 91.74, and 140.85 mg·g−1, which were higher than other reported materials with large SSAs such as graphene (GP), nanosheet/magnetite, and reduced graphene oxide (rGO). In the process of BP adsorbing MB, wrinkles were generated, and the wrinkles would further induce adsorption. BPR had fewer layers (3–5), more wrinkles, and stronger adsorption capacity (91.74 mg·g−1). The interactions between the BP-based materials and MB might cause the BP-based materials to deform, i.e., to form wrinkles, thereby creating new adsorption sites between layers, and then further inducing adsorption. Although the wrinkles had a certain promotion effect, the adsorption capacity was limited, so the sulfonic acid functional group was introduced to modify BPR to increase its adsorption sites and promote the adsorption effect. These findings could provide a new viewpoint and insight on the adsorption behavior and potential application of the BP-based materials.