Order Arrow is used to obtained faction reward.
Open faction map, you will see a list of faction (Dong Zhuo, Liu Bei, Cao Cao, etc)
Each faction has its own reward.
In this example, try clicking faction reward button, you will see thenumber of order arrow(s) you have there.
That is the list of the reward you can obtained using order arrow and good relationship. You can also get the tribute quest items here.
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