You open your inbox and click "join alliance" Actually you have to have an embassy to join an alliance. Build one then click on it, and viola, you'll get to join an alliance. After that, read the instructions.
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You can join an alliance when you have built an embassy level 1, and have invitation to the alliance from the alliance leader. You can then accept the invitation from inside the embassy.
if you build it to 100, (it costs over 1 million of each resource) you and your alliance win the game, and the game ends.
There is no Offical biggest population for Travian
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it is to activate the account on travian, to do so you need to look at the email and open the link on it