Physically-based rendering is an image synthesis technique based on simulation of physical interactions between light and surface materials. Since generated images are highly photorealistic, physically-based rendering has become an indispensable tool in advanced design visualization for manufacturing and architecture as well as in film VFX and animations. Especially, BRDF (bidirectional reflectance distribution function) is critical in realistic visualization of materials since it models how an incoming light is reflected on the surface in terms of intensity and outgoing angles. In this paper, we introduce techniques to represent BRDF as B-spline volumes and to utilize them in physically-based rendering. We show that B-spline volume BRDF (BVB) representation is suitable for measured BRDFs due to its compact size without quality loss in rendering. Moreover, various CAGD techniques can be applied to B-spline volume BRDFs for further controls such as refinement and blending.