A versatile microporous zinc(II) MOF (1) with plentiful Lewis basic sites and open metal sites synchronously has been synthesized successfully. The resultant microporous material displays excellent selectivity adsorption for small gases. The LAST selectivity values for CO2/CH4, C2H6CH4, CO2/N-2, and C3H8/CH4 are 7, 21, 38, and 125 at 101 kPa and 298 K, respectively. 1 exhibits remarkably heterogeneous catalytic performance for acid-base one-pot reactions. Furthermore, 1 exhibits recyclable selective detectability for TNP. The results illustrate that 1 is a versatile material for selective gas adsorption, cooperative catalysis, and luminescent sensing.