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The war was between China and the US, but vault Tec itself may have dropped the first bombs.
Plus they wanted to build a new society based on their most successful vault.
China launched (or more accurately dropped, since they were mostly delivered by stealthed bomber planes) their payload of nukes because the U.S. and their far superior technology (mainly power armor) was decimating them in their war for Alaska and were beginning to drop troops into China proper. The Chinese government was terrified of what would happen when the American troops finally won (which they would have unquestionably), and so decided to try to wipe them out once and for all to ensure that even if they didn't survive then their enemies wouldn't either.
Nuclear weapons in Fallout were designed for a higher radiation yield rather than an explosive one so the collective fallout of an entire nation's worth of nuclear bombs dropping on a country fuelled almost exclusively by nuclear power covered the globe in radiation and brought about the apocalypse.
The rest is history.