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Developing intrinsic self‐healing polymeric materials is of great interest nowadays to extend material lifetime and/or prevent the replacement of damaged pieces. Spontaneously humidity‐sensitive healable polymer network built around dynamic covalent B−O bonds was templated by using iminoboronate‐based boroxine derivatives. Taking advantage of the dynamic boroxine/boronic acid equilibrium and iminoboronate chemistry, it is possible to construct polymeric materials able to self‐heal without requiring any energy‐demanding external activation. Interestingly, this novel family of iminoboronate adduct‐based materials can be readily produced by a relatively simple and straightforward synthesis between boronic acid and diamine‐based compounds, paving the way to coatings that are self‐healable at ambient humidity.