Low temperature (20–230 K) spectral-luminescence studies were conducted on C60 fullerite saturated with carbon monoxide in a physisorption regime. Substantial changes in the photoluminescence characteristics of C60–CO solutions with different impurity concentrations were found already for short intercalation times. Strong dependence of the CO solubility on the saturation temperature was revealed by analyzing the contribution of “deep X-traps” to the luminescence. Furthermore, it was found that filling of the octahedral voids by CO molecules occurs with a lower gradient of the impurity distribution into the bulk C60 crystals as compared with N2. The temperature dependences of the integral emission intensity for the samples with different concentrations of carbon monoxide were studied. For the first time, using the spectral-luminescence method, it was revealed that CO molecules, in contrast to H2 and N2, exhibit a significant effect on the formation of the orientational glass and the rotational dynamics of C60 molecules. Within the model of the transfer of electronic excitation in C60 crystals, the effect of polar CO molecules on the reorientation of C60 molecules and the change in the nature of their rotation in concentrated C60–CO solutions, leading to the observed strong shift of the temperatures of orientational Tc and glass Tg transitions to lower temperatures accompanied by “blurring” of the transition boundaries, were explained.