We report a facile protocol of preparing colloidal layered double hydroxide/polyvinyl alcohol (cLDH/PVA) electrospun nanofibrous mats via direct incorporation of low-content cLDH nanoplatelets with PVA without aid of any surfactant. The as-prepared cLDH/PVA nanofibrous mats exhibit a uniform, smooth surface and enhanced temperatures of the onset decomposition and inflection compared with those of the electrospun mats of pristine PVA and solid powdery LDH/PVA (pLDH/PVA) with the same LDH content. Subsequent surface chemical modification enables the resulting cLDH/PVA fibrous mats to exhibit superhydrophobicity and adhesion to water droplets, which are distinctly different from the hydrophilicity of the unmodified cLDH/PVA fibrous mats. Our results involving the cLDH/PVA electrospun nanofibrous mats may allow designing a variety of electrospun composite nanofibers with homogeneous morphology and multiple properties.