Abstract High secondary electron yields ( σ=14–27) from polycrystalline diamond films on Mo substrates have been reported previously. We observed that continuous exposure to an electron beam degraded the secondary yield in vacuum as a function of fluence owing to a loss of surface hydrogen. However, the hydrogen partial pressure could be adjusted such that the high secondary yield remained stable during beam exposure. We have constructed a prototype electron multiplier using these diamond films for use in ultrahigh vacuum. A gain of 0.9 × 10 5 has been measured in a d.c. mode. Palladium, titanium and aluminum nitride have been studied for possible dynode substrate materials which might eliminate the need for hydrogen during operation. Total secondary yields as high as 50 were measured from diamond on palladium and σ was stable at 25 during heating at 700 K in vacuum. Raman spectroscopy and scanning electron microscopy showed that variations in σ from diamond films on Pd were due to differing concentrations of non-diamond carbon.