Number densities of atomic oxygen have been measured in pure oxygen plasma, using two-photon laser-induced fluorescence measurements. In this paper, two calibration techniques are compared: the sensitivity of the experimental setup is calibrated using scattering experiments, and reference measurements on xenon are performed using two-photon laser-induced fluorescence measurements. The theoretical background and the experimental setup are described in detail. The advantages and drawbacks are herewith outlined. Applied to high-enthalpy, pure oxygen plasma, the evaluated number densities show fairly good agreement; however, because a constant discrepancy is measured between the results when using the two calibration approaches, a systematic error is probable. Possible reasons for this error are discussed (e.g., the cross-sectional ratio, in the case of xenon reference measurement calibration). One main conclusion is that measurements that are performed using the reference measurements on xenon are preferred, because they have much fewer experimental factors to be taken into account. Nomenclature A L = laser beam area, m 2 A 21 = Einstein coefficient, s 1 E L = laser energy, J e = electron charge 1:6022 10 19 C Ft = temporal function of the laser pulse, s G a =C = preamplifier gain/capacitance ratio G PMT = photomultiplier amplification G 2 = correlation factor of the laser field _ m = mass flow, g=s n b = refraction p a = ambient pressure, Pa QE = quantum efficiency of the photomultiplier Q 21 = quenching rate, s 1 S = fluorescence, J s = reference condition sens = sensitivity of the boxcar U A = anode voltage, V V R = Rayleigh signal, V = optical efficiency = wavelength, nm = wavelength, s 1 2 ! = absorption cross section, m 4 s p = pulse time, s LT = effective lifetime, s ! = transition frequency, s 1 d= d 90 deg pol = Rayleigh cross section, m 2 ℏ = Planck constant divided by 2, 1:055 10 34 Js