Novel single-crystalline ZnO nanosheets with porous structure have been fabricated by annealing ZnS(en)_0.5 (en = ethylenediamine) complex precursor. The morphology and structure observations performed by field emission scanning electronic microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) indicate that numerous mesopores with a diameter of about 26.1 nm distribute all through each nanosheet with a high density. The transformation of structure and composition of samples obtained during thermal treatment processes were investigated by x-ray diffraction (XRD), x-ray photoelectron spectrometry (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) absorption spectroscopy. The formation mechanism of the porous structure is proposed. For indoor air contaminant detection in which formaldehyde and ammonia are employed as target gases, the as-prepared ZnO nanosheets were applied for the fabrication of gas sensors. It was found that the as-fabricated sensors not only exhibit highly sensitive performance, e.g., high gas-sensing responses, short response and recovery time, but also possess significant long-term stability. It is indicated that these ZnO nanostructures could promisingly be applied in electronic devices for environmental evaluation.