Atmospheric repetitive He discharge with 10 ns current peak width and
3
×
10
11
V s−1 voltage front rise working in jet geometry is studied. The first part of the study is devoted to electrical and optical discharge characterization including voltage-current behavior, emission dynamics, as well as ro-vibrational dynamics of N2, N
2
+
and OH molecules. It is found that He atoms get excited at the very early stage, as a result of ionization wave formation. This process follows by excitation of O, N2 and N
2
+
. It is also shown that a rather small (0.1%–1%) air admixtures facilitate gas breakdown, as revealed by shortening of the discharge current risetime. The rotational excitation of N
2
+
always overtakes He excitation by about 5 ns, with rotational temperature peaking at about 650 K and decaying afterwards, whereas rotational temperature of N2 always remains constant equal to about 300 K. This value is associated with gas kinetic temperature since the electron-rotational (e-R) excitation process is too slow, so it cannot be activated during the plasma phase and no additional change in rotational excitation of N2 happens. Nitrogen molecules remain vibrationally excited in the discharge, post-discharge and jet areas after the plasma pulse which is likely a result of ionization wave propagation. Upon water vapor injection the apparent OH rotational distributions reveal double Boltzmann slope representing thermalized and non-thermalized OH groups. Rotational temperature of the thermalized group correlates with the one of N
2
+
showing, however, much longer relaxation time, whereas for the non-thermalized group it remains above 1 eV at all conditions. The obtained results confirm that the studied ns- discharge is a good candidate for temperature-sensitive applications, such as the bio-sample treatment. Further analysis related to the ionization waves, electron density and electric field behavior is undertaken in the second part.