Currently, enterprise architecture exists on the CIO's direct staff in many companies. While this is a very important position from a strategic planning point of view, it's still weighted towards technology implementation.

I think it would be better to tie enterprise architecture and portfolio management at the hip; the former's interest is doing the right thing for the business while the latter's interest is doing the thing right for the business. Placing the combined office on the staff of the COO or CFO now makes them directly accountable to the business. This also embeds the function directly into strategic business planning and budgeting which, by design, directly "aligns IT with business." (I hate that buzzphrase)

What I have found when I have worked in an organization where there was a CIO heading up IT is that I had a great understanding of the problems we had trying to solve the business problems with technology. When I have worked in organizations where a CFO was the head of IT, I had a great understanding of the business problems we were trying to solve with technology.

Here's a skeleton from my past. In one company I worked at, we were implementing a new accounting system and IT was run by the CTO. We did it for all the usual reasons like single view of the data, faster processing, unified reporting etc. The roll-out was a marginal success. The following year, IT was headed up by the CFO after a re-org. During phase 2 of the implementation, we found out the real reasons for needing the new system included the desire close the books on the 30th or 31st of every month instead of the 35th or 36th of every month, process expense reports during the payroll period they were submitted for and to accurately forecast sales. We had a lot of re-factoring to do. The result was the revised system became a catalyst for revenue generation. The dev team-lead received a standing ovation from the sales and accounting departments at the annual company meeting.