Generation and evolution of plasma during femtosecond laser ablation of silicon are studied by steady-state and time-resolved spectroscopy in air, N2, SF6, and under vacuum. The plasma is generated faster than 200 ps (time resolution of our experiment) after excitation and mainly contains atoms and monovalent ions of silicon. Time-resolved spectra prove that silicon ions are faster than the silicon atoms which may be attributed to Coulomb repulsion and a local electric field when they are ejected from the silicon surface. During plasma evolution, ambient gas causes a confinement effect that enhances the dissociation of ambient gas molecules and the re-deposition of the removed material and leads to higher intensity and longer lifetime of the emission spectra. In SF6, a chemical reaction increases the plasma density and weakens the re-deposition effect. The different processes during plasma evolution strongly influence microstructure formation.