Potential energy surfaces are investigated for a number of low‐lying excited singlet states of methane, using a split valence plus Rydberg basis set and singly excited CI. Of the six minima found, the lowest two are valence states. The lowest minimum corresponds to the products 1 1 B 1 CH2+1 1Σ g + H2, in agreement with the observed threshold photochemistry, and is accessible by five separate routes from the lowest vertical state. The second valence minimum is a square planar structure. Of the four Rydberg minima detected, one is a local minimum on the otherwise dissociative B 1surface and two correspond closely to CH4 + structures previously determined. None of the minima have a structure from which the radical products CH3⋅+H⋅ are likely to be obtained.