Using MSTest, what is the relative path root of the DeploymentItemAttribute.
To assume that the RelativePathRoot default is the dir where your solution resides was not correct in my case, nor was RelativePathRoot defined within my .testrunconfig file. I found the RelativePathRoot default to be the /bin/debug dir for the solution.
Walking back from that point, then walking up to my file that I was attempting to deploy for the unit test worked fine.