Separating hydrocarbons from refinery dry gas is a fundamental demand in petrochemical industry. Metal-Organic Frameworks are a class of promising advanced adsorbents, yet better moisture stability and higher adsorptive selectivity are still needed to meet the requirement of petrochemical industry. Herein, a multifunctional adsorbent urea@Cu-BTC was prepared from cheap building blocks at room temperature, which exhibits generally enhanced adsorptive separation performance towards CO2/CH4, CO2/N2, C3H6/C3H8, C2H4/C2H6, CH4/N2 separation. More interestingly, urea@Cu-BTC shows significantly enhanced stability against moisture. Combining structural characterization and molecular simulation, the improved adsorptive separation performance was ascribed to the enhanced confinement from the creation of ultra-micro porosity due to the presence of urea molecule in the microporous channel of Cu-BTC. The major components in refinery dry gas can be well separated using a column filled with urea@Cu-BTC, which demonstrates that micro-regulating the channel of MOFs is a feasible strategy for preparing high performance petrochemical adsorbents.