Currently, the historical archive images of Landsat family sensors are probably the most effective data products for tracking global longitudinal changes since the 1970s. However, the issue of the degree and extent of cloud coverage is always a challenge and varies distinctively worldwide. So far, acquisition probability (AP) analyses of cloud cover (CC) of Landsat observations have been conducted with different sensors at regional scale. To our knowledge, CC probability analysis for the newly-launched Landsat-8 Operational Land Imager (OLI) across China is not reported. In this paper, monthly, seasonal, and annual APs for Landsat OLI (44,228 in total) images over China acquired from April 2013 to October 2016 with various CC thresholds were analyzed. The results showed that: first, the cumulative average APs of all OLI data over China at the CC thresholds ≤30% was about 49.6% which illustrated the availability of OLI imagery across China. Second, the spatial patterns of 10%, 20%, and 30% CC thresholds of OLI observations, coincided well with the precipitation distributions separated by the respective 200 mm, 400 mm, and 800 mm isohyetal lines. Third, the APs of images with the 30% CC threshold are the highest in autumn and winter especially in October of 58.7%, while the corresponding lowest probability occurred in June of 41.0%. Finally, the spatial differences in APs of targeted images with ≤30% CC thresholds were quite significant. At regional scales, the arid and semi-arid areas, Inland River and Songliao River basins, and northwestern side of the Hu Huanyong population line had the larger probabilities of obtaining high-quality images. Our study suggested that OLI imagery satisfy the data requirements needed for land surface monitoring, although there existed obvious spatio-temporal differences in APs over China at the 30% CC threshold.