Nanodiamond-reinforced polyurethane (NDs/PU) micro/nanofiber membrane with multifunctionality was successfully fabricated via electrospinning for the first time. The ultraviolet (UV) protection, waterproof, and tensile strength of the NDs/PU micro/nanofiber membranes with various ND additions were systematically investigated. The ultraviolet protection factor (UPF) values of NDs/PU micro/nanofiber membranes with ND contents of 5.5 and 7.5 wt % are 9317.63 and 10 111.83, respectively, which are 129.5 and 140.7 times higher than those of pure PU fiber membranes (UPF 71.36), respectively. The NDs/PU micro/ nanofiber membranes display excellent UV protection performance, which is greatly higher than the current industrial standard requirement (UPF > 40). In addition, the surface of the composite was hydrophobic, and the static water contact angle increased from 115.7°(PU reference) to 135.4°(5.5 wt % NDs/PU composite) and 139.7°(7.5 wt % NDs/PU composite). The Young's modulus, tensile strength, and elongation at break were increased by 29%, 105%, and 66% with the addition of 5.5 wt % NDs. The multifunctional NDs/PU micro/nanofiber membranes display good surface morphology, excellent UV protection performance, water resistance, and tensile strength, with great potential in the multifunctional textiles and smart wearables.