A highly efficient homogeneous catalyst system for the production of CH3OH from CO2 using pentaethylenehexamine and Ru-Macho-BH (1) at 125-165 °C in an ethereal solvent has been developed (initial turnover frequency = 70 h(-1) at 145 °C). Ease of separation of CH3OH is demonstrated by simple distillation from the reaction mixture. The robustness of the catalytic system was shown by recycling the catalyst over five runs without significant loss of activity (turnover number > 2000). Various sources of CO2 can be used for this reaction including air, despite its low CO2 concentration (400 ppm). For the first time, we have demonstrated that CO2 captured from air can be directly converted to CH3OH in 79% yield using a homogeneous catalytic system.