A new autonomous water-enabled self-healing coating with antibacterial-agent-releasing capability was developed for the first time by precipitating an aqueous solution of hydrogen-bonded tannic acid (TA) and polyethylene glycol (PEG) (TA: 5 mg/mL; PEG: 5 mg/mL with MW = 100 kDa) to form a smooth, uniform coating layer with an average roughness of 0.688 nm and thickness of 22.3 μm on a polymethyl methacrylate (PMMA) substrate after 10 min of incubation. Our method is cost- and time-efficient, as the hydrophilic coating (water contact angle = 65.1°) forms rapidly, binding strongly to the PMMA substrate (adhesive energy = 83 mJ/m2), without the need for pretreatment or surface modification, and is capable of rapid self-repair (approximately 5 min) through hydrogen bonding in aqueous media. Furthermore, adding 0.5 mg/mL of chlorhexidine acetate (CHX), a commonly used antibacterial agent in dentistry, into the TA–PEG emulsion allowed the release of 2.89 μg/mL of the drug from the coating layer, which is promising for actively inhibiting the vitality and growth of bacteria around PMMA dental restorations. The use of CHX-loaded TA–PEG hydrogen-bonded complexes is highly favorable for the fabrication of an autonomous self-healing biocoating with active antibacterial-agent-releasing capability, which can be applied not only in dentistry but also in other medical fields.