This inquiry is not intended to start a political discussion. Where/how did Valerie Jarret and Susan Rice accumulate their wealth? Did they marry into it? I can’t imagine they could have accumulated so much working for various governmental agencies. I’m also not aware of any long-term private sector employment.
What wealth specifically? Your post is a little odd, since it seems to assume that we’re familiar with the wealth of two relatively mid-level gov’t officials (granted Rice has been in the news lately, but I don’t think I’ve heard any stories about her finances). I imagine Rice is well-off, but I doubt she’s super-wealthy or anything. Do you have a cite that states otherwise.
Jarret was CEO of a real-estate company during the 90’s, and left several years before the real-estate bubble popped. So to the extent that she’s rich, I’d imagine that accounts for most of it.
I have been reading in the 20m range, which does seem like a lot to me. 
ETA: put the wrong smile face
Apparently Jarret spent over a decade as an executive (including a stint as CEO) of a real estate development company, and also served on the board of the Chicago stock exchange.
Rice apparently has worked in consulting and advising at firms such as McKinsey and Intellibridge. Her husband also seems to have done quite well for himself.
That wiki article says from mid 1990 until graduating in 1992 for McKinsey. Doubt the wealth came from that but who knows.
She seems to have spent most of the interm between Clinton and Obama at foreign policy think-tanks. I imagine those places pay pretty well to have a former Asst. SoS there, so I’d suspect that plus her husbands money from ABC accounts for it.
The rumor is that Rice inherited 20 mil or so from her rich dad. Supposedly hubby also had family money.