The development of efficient systems for selective aerobic oxidation of hydrocarbons and alcohols to produce more functional compounds (aldehydes, ketones, acids or esters) with atmospheric air or molecular oxygen is a grand challenge for the chemical industry. Here we report the synthesis of palladium nanoparticles supported on novel nanoporous nitrogen-doped carbon, and their impressive performance in the controlled oxidation of hydrocarbons and alcohols with air. In terms of catalytic activity, these catalysts afford much higher turnover frequencies (up to 863 turnovers per hour for hydrocarbon oxidation and up to ~210,000 turnovers per hour for alcohol oxidation) than most reported palladium catalysts under the same reaction conditions. This work provides great potential for the application of ambient air and recyclable palladium catalysts in fine-chemical production with high activity.