A multifunctional, electrospun, ultrathin face mask is desirable for preventing disease spread while ensuring breathability. However, balancing ultrathin construction with antimicrobial efficacy is challenging. Here, we fabricated an ultrathin micro/nanofibrous electrospun matrix, consisting of three biodegradable polymer layers, for high antibacterial efficiency, breathability, and biodegradability. The outer layer, with an average thickness of 9.01 ± 3.1 μm, is composed of polycaprolactone (PCL), silver nitrate (AgNO₃), and β-cyclodextrin (β-CD). The middle layer, with a thickness of 4.61 ± 1.4 μm, comprises poly(vinyl alcohol) (PVA) and multiwalled carbon nanotubes (MWCNT) as a conductive layer. The inner layer, with a thickness of 5.12 ± 1.4 μm, contains PVA, carboxymethyl chitosan (CMC), and cellulose nanofibrils (CNFs) as a superabsorbent layer, supported by medical gauze. With a total thickness of ∼300 μm, the mask provides antibacterial efficacy, self-cleaning, reusability, mechanical stability, and biodegradability. This design advances filtering face masks, offering a solution to combat contagious diseases while minimizing environmental impact.