The 355 nm laser pulse from THG (Third Harmonic Generation) of a Q-switched Nd3+∶YAG laser was used to ablate silicon mounted in air. The time-and space-resolved optical emission spectra were measured for different pulse energy in the wavelength range of 380-420 nm, the emission spectra of N+ was found for impact ionization of air near target surface on the early stage of plasma plume expansion. Under the model of local thermodynamic equilibrium, the electronic temperature of plasma was deduced to be in the range of 18 000-40 000 K using the Saha equation by the relative line intensities, and the electron density was deduced to be in the 1017 cm-3 scale by FWHM (the full width at half maximum) of Si spectral lines, the temporal and spatial evolution of the electronic temperature and electron density was given, showing that the electronic temperature and electron density exhibited second order exponential decreasing with laser delay time and a Lorentz distribution in space. The reason for the spatial position deviation of the maximum electron density from the maximum spectral intensity was analyzed. The relationship between the plasma plume parameters and laser pulse energy was discussed.