The volume $V$ of a cube, defined by the formula $V = a^3$ where $a$ is the side length, is given as $V=64$ cm³. Therefore, the side length is calculated as: \[a = \sqrt[3]{64} = 4 \text{ cm}.\] The space diagonal $d$ of the cube, representing the longest distance between opposite vertices, is determined using the three-dimensional Pythagorean theorem: \[d = a \sqrt{3} = 4 \sqrt{3} \text{ cm}.\]