Mesoscale volumetric imaging is of great importance for the study of bio-organisms. Among others, optical projection tomography provides unprecedented structural details of specimens, but it requires fluorescence label for chemical targeting. Raman spectroscopic imaging is able to identify chemical components in a label-free manner but lacks microstructure. Here, we present a dual-modality optical-Raman projection tomography (ORPT) technology, which enables label-free three-dimensional imaging of microstructures and components of millimeter-sized samples with a micron-level spatial resolution on the same device. We validate the feasibility of our ORPT system using images of polystyrene beads in a volume, followed by detecting biomolecules of zebrafish and Arabidopsis, demonstrating that fused three-dimensional images of the microstructure and molecular components of bio-samples could be achieved. Last, we observe the fat body of Drosophila melanogaster at different developmental stages. Our proposed technology enables bimodal label-free volumetric imaging of the structure and function of biomolecules in a large sample.