Supporters say the move is justified by sky-high living costs in the Alpine nation, but surveys suggest Switzerland will say "No thanks" to a minimum wage so high it could pass for a mid-management salary elsewhere.
The Swiss will also be voting on a multi-billion-dollar deal to buy fighter jets from Sweden, and are almost certain to back measures to ban paedophiles from working with children.
Most voting stations open at 10:00 am (0800 GMT) and are set to close at noon, with an early estimate of the results expected soon afterwards.
Much of the national debate ahead of today's vote has focused on the pros and cons of introducing a minimum wage.
The unions behind the "Decent Salary" initiative insist at least 22 Swiss francs (USD 25, 18 euros) an hour, or 4,000 francs (USD 4,515, 3,280 euros) a month, is needed to survive in Switzerland, one of the world's most expensive countries.
If the voters agree, the small nation nestled in the heart of Europe, would go from having no minimum wage to boasting the world's highest, far above the USD 7.25 in the United States, 9.43 euros in France, 5.05 euros in Spain and the recently agreed 8.00 euros in Germany, set to take effect next year.
Opponents have warned a minimum wage, and especially such a high one, would deal a death blow to many businesses and would weaken Switzerland's healthy economy.
Supporters counter that higher basic wages would boost the purchasing power of some 330,000 people, or one in 10 employees in the country.
People working in sales, services and farming, or as hairdressers and flight attendants, for instance, generally earn far less than the proposed minimum wage.
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