Electron and negative ion densities in the afterglow and in the plasma initiation phase of a 13.56-MHz rf discharge in CF4 were measured by using a microwave cavity method and a laser photodetachment technique. Measurements were carried out at low rf powers (¿10 W) and in the pressure range from 100 to 300 mTorr. The electron density in the afterglow showed an enhanced decay rate due to the presence of negative ions. Electrons originating from negative ions through associative collisional detachment with neutral radicals were also detected in the afterglow. Decay curve analysis of the negative ion density gave an ion–ion (presumably CF+3-F-) recombination rate constant of (5±2)×10-13 m3¿s-1, and showed that, in the active plasma, the negative ion loss rates by associative detachment and ion–ion recombination are of the same order of magnitude. The behavior of the electron and negative ion densities in the plasma initiation phase indicates that molecules and radicals that slowly accumulate in the plasma do not play a significant role in the production of negative ions.