Developing wearable articles with radiation protection safety and wear comfort is one of the urgent issues in that flourishing nuclear technologies are accompanied by increasing radiation threats. However, current wearable articles either display insufficient shielding performance or exhibit poor air and water vapor permeability, which are difficult to meet the growing demand of personal protection in nuclear environments. In this paper, polymaleic acid (PMA) and di(dioctylpyrophosphato) ethylene titanate (DPET) have been used to superficially modify boron carbide (B4C) particles for constructing sufficient hydrogen bonds with polyvinyl alcohol (PVA) matrix. Synergistic effects of PMA and DPET lead to enhanced interfacial interaction. As high as 55 wt% B4C/PVA fibers have been obtained with smooth wet spinning. Their multi-layered fabrics display excellent air and water vapor permeability meanwhile thermal neutron shielding. Three-layer B4C/PVA fabrics have 89.2 % thermal neutron (0.025 eV) shielding rate. In addition, 321.1 mm/s air and 2236.2 g/m2·24 h water vapor permeability have been measured. Besides, the fabrics still show great flexibility in spite of the fibers with extreme filling of inorganic particles. This work provides alternative wear articles to cope with the dilemma of radiation protection safety and wear comfort in neutron radiation environments.