The potential for dual-calibrated fMRI to provide quantitative estimates of physiological parameters has been increasingly investigated. We present a novel analysis methodology to estimate capillary (CBVcap) and venous (CBVv) blood volumes. These parameter estimates are made in addition to standard physiological parameters (cerebral blood flow (CBF), oxygen extraction fraction (OEF), and cerebral metabolic rate of oxygen (CMRO2)). Maps of CBVcap demonstrate a marked reduction in the appearance of large vessels (compared to CBVv data) and show significant correlations with CBF and CMRO2. These findings suggest an important role for CBVcap for assessing cerebral metabolic function and neurovascular coupling.