5-(1H-Tetrazol-1-yl)isophthalic acid (H2L) reacts with Cu(II) ion forming a new metal-organic framework {[CuL]center dot DMF center dot H2O}(infinity) (1) (DMF = N,N-dimethylformamide), with a rutile-related type net topology. Compound 1 possesses a 3D structure with 1D channels that can be desolvated to yield a microporous material. Adsorption properties (N-2, H-2, O-2, CO2, and CH4) of the desolvated solid [CuL] (1a) have been studied, and the results exhibit that la possesses fairly good capability of gas sorption for N-2, H-2, O-2, and CO2 gases, with high selectivity ratios for O-2 over H-2 at 77 K and CO2 over CH4 at 195, 273, and 298 K. Furthermore, la has excellent O-2 uptake at 77 K and a remarkably high quantity of adsorption for CO2 at room temperature (298 K) and atmospheric pressure, suggesting its potential applications in gas separation or purification.