The discharge characteristics of capacitively coupled argon plasmas driven by very high frequency discharge are studied. The mean electron temperature and electron density are calculated by using the Ar spectral lines at different values of power (20 W–70 W) and four different frequencies (13.56 MHz, 40.68 MHz, 94.92 MHz, and 100 MHz). The mean electron temperature decreases with the increase of power at a fixed frequency. The mean electron temperature varies non-linearly with frequency increasing at constant power. At 40.68 MHz, the mean electron temperature is the largest. The electron density increases with the increase of power at a fixed frequency. In the cases of driving frequencies of 94.92 MHz and 100 MHz, the obtained electron temperatures are almost the same, so are the electron densities. Particle-in-cell/Monte-Carlo collision (PIC/MCC) method developed within the Vsim 8.0 simulation package is used to simulate the electron density, the potential distribution, and the electron energy probability function (EEPF) under the experimental condition. The sheath width increases with the power increasing. The EEPF of 13.56 MHz and 40.68 MHz are both bi-Maxwellian with a large population of low-energy electrons. The EEPF of 94.92 MHz and 100 MHz are almost the same and both are nearly Maxwellian.