A non-aligned country does not lock itself to one of the world’s powerful sides. The famous use is from the Cold War: some countries would not stand with the United States or with the Soviet Union, and they called themselves the Non-Aligned Movement. Though actually, “not joining a side” never meant “having no friends and no deals.” Many of those countries still took help, sold goods, or talked with both camps. Today people still use the word for a country that tries not to tie itself to one superpower. It is a serious news-and-history word, not an everyday one. You would not normally call a person non-aligned unless you were joking about politics.