Step 1: Understanding the Concept:
A cube of 64 small cubes implies a $4 \times 4 \times 4$ structure. The distribution of paint on the faces determines the coloring of the small internal and external cubes.
Step 2: Detailed Explanation:
1. Total cubes = 64, so the side of the large cube is $n = \sqrt[3]{64} = 4$.
2. Based on the description (Red on two adjacent faces and one opposite to one of them, Yellow on two opposite, etc.), there are effectively 4 faces painted Red (Front, Back, Left, Right) if we consider the phrasing "two adjacent and one opposite sides face" as covering the vertical faces.
3. For an $n=4$ cube, the center cubes of any face are $(n-2) \times (n-2) = (4-2) \times (4-2) = 2 \times 2 = 4$ cubes.
4. These center cubes on a face have only one face painted, and it is the color of that large face.
5. If there are 4 faces painted red, then the total number of cubes with only one red face (and no other colors) is:
Number of red faces $\times$ Center cubes per face = $4 \times 4 = 16$.
Step 3: Final Answer:
There are 16 cubes that have one red colored face only.