In the present research, experiments on the formation and retention of nanoparticles (NPs) in the plasma of radio frequency (RF) capacitive discharge in acetylene were carried out with vertically positioned internal electrodes. It has been shown via SEM and TEM techniques that NPs found on the horizontal tube wall after the discharge operation have a spherical shape with a predominant diameter of approximately 400−600 nm. HRTEM analysis reveals their amorphous structure. At the same time, such NPs were not found on vertical electrodes, only a polymer film was deposited. To elucidate the possibility of NPs leaving the plasma in the direction of vertical electrodes, a model of NP retention in the near-electrode sheath of an RF capacitive discharge was elaborated. The model has shown that nanometer-and even micrometer-sized particles formed in the plasma cannot cross the near-electrode sheath and reach the electrode surface. For the plasma consisting of three charged components (positive ions, electrons, and NPs), an analytical model of ambipolar diffusion was developed. Applying this model, it has been shown that the ambipolar electric field can keep the micrometer-sized NPs in the plasma if their concentration is low. However, in the case of a high concentration of NPs, they can be retained with a diameter of no more than a few hundred nanometers due to a significant decrease in the ambipolar electric field. The calculation results are in agreement with our experimental data.