The effect of surface Mo coating on the high-current electron emission performances for polymer velvet cathode has been investigated in a diode with A-K gap of 11.5 cm by the combination of time-resolved electrical diagnostic and temporal pressure variation. Compared with uncoated polymer velvet cathode under the single-pulsed emission mode, the Mo-coated one shows lower outgassing levels ($0.40 Pa L), slower cathode plasma expansion velocity ($2.30 cm/ls), and higher emission stability as evidences by the change in cathode current, temporal pressure variation, and diode perveance. Moreover, after Mo coating, the emission consistency of the polymer velvet cathode between two adjacent pulses is significantly improved in double-pulsed emission mode with $500 ns interval between two pulses, which further confirms the effectiveness of Mo coating for enhancement of electron emission performance of polymer velvet cathodes. These results should be of interest to the high-repetitive high-power microwave systems with cold cathodes. V C 2013 AIP Publishing LLC. [http://dx.