A system and a method of Zigbee communication for actively selecting and accessing a Zigbee network. The Zigbee communication system includes multiple Zigbee coordinators forming multiple Zigbee networks for transmitting information on services of end-devices currently accessing each of the formed multiple Zigbee networks; and an end-device for receiving the information on the services, analyzing the received information on the services, selecting a predetermined one of the multiple Zigbee networks based on results of the analysis, and accessing the selected Zigbee network. Accordingly, the end-device can search services provided by other end-devices over a Zigbee network without gaining access to the Zigbee network, thereby reducing unnecessary resource consumption and wasted time caused by accessing and exiting each Zigbee network by a conventional end-device for service search.