with only this limited information, ensure the following process.
1. with an Image open go: Edit > Assign Profile
2. In the Assign Profile Window, select the Radio Button for "Profile", then in the dropdown menu select "sRGB IEC61966-2.1"and click "OK" button.
3. Open the Color Picker Window by Double-Clicking on the foreground color in the Tools Panel, or Color Panel
4. Hover your cursur over the area of the image you want to sample
5. Look in the top bar of Photoshop, The dropdown for "Sample Size" should say "Point Sample"— this means photoshop is only looking at the exact 1 pixel that the cursor is on. If it says any other options "3 by 3 Average" "5 by 5 Average" "11 by 11 Average""31 by 31 Average" "51 by 51 Average" "101 by 101 Average" then you may not get the exact reading you're hoping for as photoshop is now thinking to look at the clusters of pixels around where you're hovering.
6. Click the cursor to sample the color
7. The color Picker Window will then show the color sampled and select the HEX code (found at the bottom of the window, below the RGB values.
Since I assumed this is going for a color you want to use on a website as well, use the HEX code rather than specifying RGB color values in your HTML/CSS
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