Oxygen quantification in trace amounts is essential in many fields of science and technology. Optical oxygen sensors proved invaluable tools for oxygen measurements in a broad concentration range, but until now neither optical nor electrochemical oxygen sensors were able to quantify oxygen in the sub-nanomolar concentration range. Herein we present new optical oxygen-sensing materials with unmatched sensitivity. They rely on the combination of ultra-long decaying (several 100 ms lifetime) phosphorescent boron- and aluminium-chelates, and highly oxygen-permeable and chemically stable perfluorinated polymers. The sensitivity of the new sensors is improved up to 20-fold compared with state-of-the-art analogues. The limits of detection are as low as 5 p.p.b., volume in gas phase under atmospheric pressure or 7 pM in solution. The sensors enable completely new applications for monitoring of oxygen in previously inaccessible concentration ranges.