To contribute to the debate as to whether volunteering is an outcome of democratization rather than a driver of it, we analyze how divergent democratization pathways in six countries of the former Soviet Union have led to varied levels of volunteering. Using data from the European Values Study, we find that Latvia, Lithuania, and Estonia—which followed a Europeanization path—have high and increasing levels of civil liberties and volunteering. In Russia and Belarus, following a pre-emption path, civil liberties have remained low and volunteering has declined. Surprisingly, despite the Orange Revolution and increased civil liberties, volunteering rates in Ukraine have also declined. The case of Ukraine indicates that the freedom to participate is not always taken up by citizens. Our findings suggest it is not volunteering that brings civil liberties, but rather that increased civil liberties lead to higher levels of volunteering.