User groups can be utilized to assign policies and/or Shared Folders. From the 'User Groups' sub-tab you are able to create user groups manually within LastPass Enterprise. Alternatively, for those that have elected to use the LastPass AD client, the client can be configured to sync user groups automatically from your active directory.
To manually create a new group simply hit Add Group and type in the name of the Group, for example, 'Executive Team' or 'Marketing'. Then simply move the appropriate employees from column A to column B, and hit 'Save'. Once the group has been saved, you can jump to either policies or Shared Folders, and assign either to the group accordingly.