A novel preparation technique termed “Chemical Annealing (CA)” was developed with aim of making a stable and rigid structure of Si-network. The a-Si:H films were made by the alternate deposition of several tens angstrom thick a-Si:H and the treatment with atomic hydrogen or excited novel gases such as Ar* and He*. Hydrogen contents (CH) and optical gap (Eg) in the film prepared by this tecnique were able to reduced by CH of 1.5at%, and Eg of 1.5eV, respectively at substrate temperature:300C. All of them exhibited high photoconductivities in the level of 10-5 10-4 S/cm under illumination of 100mW/cm2. In the films with CH of 3at% or less, in particular, marked improvement was confirmed in the stability after light soaking. In addition, the time-of-flight measurement revealed a non-dispersive transport and a significant enhancement in the drift mobility of holes up to 0.2cmm2/Vs at room temperature in the film with CH : 5at% and Eg:1.65eV prepared at 300C. Advantages of the CA process are summarized together with the discussion of role of atomic hydrogen, excited novel gases such as Ar* and He* in the growing surface.