In this paper, experimental results obtained with laser-induced plasma spectroscopy to retrieve local compositions are presented for an ambient pressure up to 5.0 MPa in a still cell. Well-controlled mixtures of gases are introduced and plasma is obtained with the fundamental emission of a pulsed Nd:YAG laser. Simultaneously, plasma shape and spectrally resolved data are taken with a temporal resolution down to 2 ns. First, the temporal evolutions of a high-pressure nitrogen plasma are analyzed as function of spark energy. It is shown that plasma changes orientation from an elongated shape parallel to the laser line to a perpendicular one in a very short time. Results are reported for both spatial and spectral variations. Afterward, the effects of increased carbon concentration are discussed in both shape and spectra. It is seen that strong intensity due to the atomic carbon emissions appear for the high-pressure case. From those experiments, calibration strategies are proposed to get equivalence ratio under high-pressure conditions with a ratio of carbon versus nitrogen and oxygen. The delay between plasma and measurements is set to 2,000 ns and the signal is integrated for 5,000 ns, so as to yield a good signal to noise ratio and a good sensitivity of the technique to changes in mixture fraction. Calibration curves are reported for equivalence ratio up to 1.00 and for pressure from 1.0 to 5.0 MPa. It is shown that typical uncertainties are limited to 7.5% regardless the equivalence ratio in a single shot approach using a spectral fit procedure, whereas it accounts to two times more in a more classical peak ratio approach. Increasing the pressure tends to increase the precision as lower pressure had higher uncertainties.