Every ETF has a Net Asset Value (NAV) of underlying constituents at a given time. You can see the NAV listed on the fact sheet for a given ETF.
The market price is usually very close to the NAV. If the ETF trades at a discount, arbitragers will step in to buy shares then sell the basket of underlying holdings. If at a premium, they'll short ETF shares & buy the underlying holdings. The arbitragers are either market makers or super-sophisticated algo type shops. Big volume, penny profits, not something to try at home. In a nutshell, the free market system itself keeps the prices pretty close to parity.
It's not perfect, but it generally works out. For example, the NAV of VTI closed yesterday at 93.70 and the market price was 93.68.