Hmmmm... With little forethought and rather off the cuff:
For me, it is the sharing of the most personal thoughts, feelings, and experiences (emotional intimacy) between two people. Sexual initmacy is the expression of that in a physical form. Sexual initmacy is more than sex for sex's sake, but rather is experienced when emotional intimacy is reached between two people.
So, I guess we can have intimate conversations (such as between us on this BB) and have intimate sex, but one does not necessarily follow the other; however, emotional initimacy is necessary for truly intimate sex.