An analytical and numerical study is presented to show that buoyancy-opposed mixed convection in a vertical porous duct with circular cross-section is unstable. The duct wall is assumed to be impermeable and subject to a uniform heat flux. A stationary and parallel Darcy's flow with a non-uniform radial velocity profile is taken as a basic state. Stability to small-amplitude perturbations is investigated by adopting the method of normal modes. It is proved that buoyancy-opposed mixed convection is linearly unstable, for every value of the Darcy-Rayleigh number, associated with the wall heat flux, and for every mass flow rate parametrised by the P,clet number. Axially invariant perturbation modes and general three-dimensional modes are investigated. The stability analysis of the former modes is carried out analytically, while general three-dimensional modes are studied numerically. An asymptotic analytical solution is found, suitable for three-dimensional modes with sufficiently small wave number and/or P,clet number. The general conclusion is that the onset of instability selects the axially invariant modes. Among them, the radially invariant and azimuthally invariant mode turns out to be the most unstable for all possible buoyancy-opposed flows.