This invention relates to novel chemical resistant, film forming, and moisture vapor permeable ionomers, including specialized polyurethane ionomers, polyurea ionomers, polyamide ionomers, polyester ionomers, or a mixture of the said ionomers, having high content of covalent-bonded ionic groups, total >100 milli-equivalents per 100 gram of ionomers. These specialized ionomers have low noxious chemical crossover rate, high moisture vapor transmission rate, hydrolytically stable in humid environment, and capable of forming thin films. These novel chemical resistant ionomers can be cationic (selected from tertiary amines and their derivatives or quaternary ammoniums), anionic (selected from aliphatic carboxylic acids and their derivatives or aliphatic sulfonic acids and their derivatives), or zwitterions (selected from ionomers or a mixture of ionomers containing both cations and anions groups), or a mixture of any combination of the above three types, preferably in a form of coating solutions or dispersions suitable for coatings to form thin films or membranes, to protect the coated surface with acceptable barrier properties at any humidity with high moisture vapor permeability. One major application is in the field of protective fabric and protective clothing, gloves, shoes, hats, tents, sleeping bags, and protective skin cream against noxious liquids and gases.