Yes, but will take a few short reversal steps.
We must presume you have the sf::Image of which to get the pixel information.
I will also presume you mean a rotated sf::RectangleShape...
1) get the global point position (i.e. the position that you want to sample)
2) use the rectangle's inverse transform to transform that point (you are now in local space - the rectangle is 0, 0 to rectangleSize.x, rectangleSize.y) - this may be enough information and you can stop here...
3) to find the ratio of the point within that rectangle, divide the point components (x and y) by the rectangle's size components
4) multiply those component ratios (x and y) with the respective texture rectangle size components
5) add the texture rectangle position/top-left (if zero, this can obviously be skipped)
You now have the co-ordinate in the texture that was at that point on the screen.
To get its colour, use that co-ordinate on the matching sf::Image (getPixel). If the texture or image is only a cropped part of the other, you will need to add/subtract that offset.