How did the motorcycle emissions evolve during the economic development in China? To address data gaps, this study firstly measured the volatile organic compound (VOC) and intermediate-volatility organic compound (IVOC) emissions from motorcycles. The results confirmed that the emission control of motorcycles, especially small-displacement motorcycles, significantly lagged behind other gasoline-powered vehicles. For the China IV motorcycles, the average VOC and IVOC emission factors (EFs) were 2.74 and 7.78 times higher than the China V–VI light-duty gasoline vehicles, respectively. The notable high IVOC emissions were attributed to a dual influence from gasoline and lubricating oil. Furthermore, based on the complete EF dataset and economy-related activity data, a county-level emission inventory was developed in China. Motorcycle VOC and IVOC emissions changed from 2536.48 Gg and 197.19 Gg in 2006 to 594.21 Gg and 12.66 Gg in 2020, respectively. The absence of motorcycle IVOC emissions in the existed vehicular inventories led to an underestimation of up to 20%. Across the 15 years, the motorcycle VOC and IVOC emission hotspots were concentrated in the undeveloped regions, with the rural emissions reaching 5.81–10.14 times those of the urban emissions. This study provides the first-hand and close-to-realistic data to support motorcycle emission management and accurate air quality simulations.