Yes, and it's often the best choice. Cathedral ceilings need both thermal performance and air sealing in tight rafter cavities; spray foam handles both. Cincinnati installs typically use closed-cell at 4-6" depth.
More detail
Cathedral ceilings (vaulted ceilings without an attic above) are difficult to insulate well with conventional materials because rafter cavities are typically only 6-10 inches deep, the cavity must hold both insulation and a ventilation channel (in vented assemblies), and any air leakage in the ceiling plane creates ice dams in winter. Closed-cell foam fills the cavity completely, air-seals the ceiling plane, and acts as a vapor retarder, eliminating the need for separate ventilation in many cases (creating an "unvented hot roof" assembly). Cincinnati Climate Zone 4 unvented hot-roof assemblies need foam-only insulation totaling at least R-49 or hybrid approaches that combine closed-cell foam at the roof deck with batting or open-cell below. Our Cincinnati installers handle both vented (closed-cell to leave a soffit-to-ridge ventilation channel) and unvented designs depending on the specific home. Cincinnati cathedral-ceiling retrofit pricing: typical 1,200-1,800 sqft Cincinnati cathedral runs 4,800-7,200 board feet of closed-cell foam at $1.85 average = $9,000-$13,500 fixed. The work runs 1-2 days. The biggest determinant of cost is rafter access (open-rafter cathedrals are simpler than enclosed-rafter assemblies that require partial drywall removal). Our Cincinnati installers scope this during the on-site assessment.