Biocompatible coatings that can protect metal implants have great potential in tissue engineering. In this work, MWCNT/chitosan composite coatings with hydrophobic-hydrophilic asymmetric wettability were facilely prepared by one-step in situ electrodeposition. The resultant composite coating exhibits excellent thermal stability and mechanical strength (0.76 MPa), benefiting from the compact internal structure. The thickness of the coating can be controlled precisely by the amounts of transferred charges. The MWCNT/chitosan composite coating demonstrates a lower corrosion rate due to its hydrophobicity and compact internal structure. Compared with exposed 316 L stainless steel, its corrosion rate is reduced by two orders of magnitude from 3.004 × 10−1 mm/yr to 5.361 × 10−3 mm/yr. The content of iron released from 316 L stainless steel into the simulated body fluid drops to 0.1 mg/L under the protection of the composite coating. In addition, the composite coating enables efficient calcium enrichment from simulated body fluids and promotes the formation of bioapatite layers on the coating surface. This study contributes to furthering the practical application of chitosan-based coatings in implant anticorrosion.