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there's a little parking lot (about 4 or 5 spaces) off of GW Parkway, right near the 395 intersection. backdrop? potomac river, and the washington/jefferson monuments. plus you have the cherry blossoms in the background and everything. i've always wanted to take pics there on a sunny day. you'd have to do it during the week though, around like 11am or so. to avoid traffic.
There's a gas station to the left of the stair if you are facing it but the stairs itself has a little lot on the bottom where you can park sideways and get a good shot of the car with the stairs in the background.