Using a simple analytical model, together with a 1D particle-in-cell simulation, we show that it is possible to generate an asymmetric plasma response in a sinusoidally excited, geometrically symmetric, capacitively coupled plasma (CCP). The asymmetric response is produced using rf electrodes of differing materials, and hence different secondary electron emission coefficients. This asymmetry in the emission coefficients can produce a significant, measurable dc bias voltage (Vbias /Vrf ∼ 0–0.2), together with an asymmetry in the plasma density profiles and ion flux to each electrode. The dc bias formation can be understood from a particle-flux balance applied to each electrode, and results from two main effects: (1) the larger effective ion flux at each electrode due to the emission of secondary electrons and (2) ion-flux multiplication within the sheath due to ionization from these emitted secondary electrons. By making use of an empirical fit to the simulation data, the possibility of non-invasively estimating secondary electron emission coefficients in CCP systems is discussed.