Abstract The results of a systematic study of chalcogen adsorption on Ni(111) utilizing angular resolved photoemission illuminate several interesting trends in the bond formation. The unique feature of polarized and variable photon energy from synchrotron radiation is used to resolve effectively some of the spectral features. These trends are detectable due to a unique ability to resolve spectroscopically the splitting of the degeneracy of the adsorbate p levels for a sequence of adsorbate-elements. The position and symmentry of the (p x , p y ) and p z adsorbate derived bands at Γ are evaluated for a variety of ordered chalcogen overlayers. A likely interpretation for producing the observed splitting is illustrated by the results of a tight binding model calculation on an hexagonal net. Treatment of the quadratic net reveals interesting conclusions that for a c(2 × 2) overlayer the (p x ,p y ) level is non-bonding at Γ .