The basic sites of various oxide catalysts for the oxidative dimerisation of methane were studied by FTIR spectroscopy of adsorbed molecular probes (chloroform and CO2). The methods used are compared and the advantage of CO2 as probe for specifying the basic sites is demonstrated. The strengths of the basic sites were seen to correlate with the spectral parameters of the surface carbonates. Differences in spectral responses of carbonates are attributed to the different states of oxygen participating in their formation. The concentration of the strongest sites was estimated. A study of the catalytic activity of this system indicates that the system's activity in oxidative methane coupling depends on the presence and concentration of strong basic sites on the catalyst surface.