In this work we have performed Ultraviolet Photoelectron Spectroscopy (UPS) and X-Ray Photoelectron Spectroscopy (XPS) on: (i) 40Å of Ru deposited on 20Å of ALD-HfO2 (Ru-HfO2), (ii) 40Å of Re deposited on 20Å of ALD-HfO2 (Re-HfO2), and (iii) 40Å of W deposited on 20Å of ALD-HfO2 (W-HfO2) in as deposited as well as after 600˚C in-situ anneal exposure. The samples with Ru and Re indicated significant reduction in the oxygen content and shift in the Hf peaks towards higher binding energy after anneal as compared to the as deposited state. The loss of oxygen after anneal was associated with the reduction in the surface work function of Ru and Re measured by UPS. However, the sample with W showed a redistribution of oxygen after anneal leading to the formation of multiple oxides of W having a net higher surface work function. The spectroscopic measurements were correlated with the electrical measurements made on MOS capacitors with Ru metal gates on HfO2 gate dielectric. The results indicated that the oxygen content at metal/high-k interface plays an important role in governing the effective work function of Ru on HfO2 gate dielectric.