Active microwave measurements have the potential to estimate vegetation optical depth (VOD), an indicator related to vegetation water content and biomass. The Advanced SCATterometer (ASCAT) provides long-term C-band backscatter data at vertical-vertical (VV) polarization from 2007. So far, very few studies have considered retrieving VOD from this active sensor. This study presents a new publicly released global long-term and continuous (2007–2020) C-band VOD dataset retrieved from the ASCAT observations, named the ASCAT INRAE-BORDEAUX or ASCAT IB VOD product. The retrieval algorithm is based on the Water Cloud Model (WCM) including the Ulaby bare soil model. The algorithm takes advantage of a multi-temporal (MT) retrieval method relying on a cost function where constraints to the retrieved parameters are implemented and a reanalysis soil moisture (SM) dataset from ERA5-Land is used as an input. The performance of ASCAT IB VOD was evaluated by inter-comparing it with ASCAT Technische Universität Wien (TUW), the Advanced Microwave Scanning Radiometer 2 (AMSR2), and VOD Climate Archive (VODCA) VOD products (the last two products are estimated from passive microwave observations). Results showed that ASCAT IB VOD presented the highest spatial correlation with aboveground biomass (R ∼ 0.83) and with the Global Ecosystem Dynamics Investigation (GEDI) canopy height (R ∼ 0.84–0.85). In terms of temporal performance, ASCAT IB VOD had the highest correlation R values with leaf area index (LAI) and Normalized Difference Water Index (NDWI) in most parts of the globe from 2013 to 2018. This contrasts with AMSR2 VODs which correlated better with Normalized Difference Vegetation Index (NDVI). The new ASCAT-based VOD product on a global scale highlighted the potential benefit of combining active (namely ASCAT) and passive (namely AMSR2) VOD products for vegetation studies.