Another geometrical relation does allow you to inscribe an octahedron inside an icosahedron. The vertices of the octahedron lie on edge centers, not on vertices, of the icosahedron.
Select any vertex $A$ of the icosahedron. The five nearest vertices to $A$ form a regular pentagonal ring; render these vertices $B,C,D,E,F$ in rotational order around the ring.
Now connect, let us say, the midpoint of the "spoke" $\overline{AB}$ with the midpoint of the opposite ring edge $\overline{DE}$. This connection spans exactly $90°$ of arc on the inscribed or circumscribed sphere and thus qualifies as an octahedral edge.
Since there are five ways to orient this connection around each of twelve vertices of the icosahedron and the octahedron has twelve edges, there must be five inscribed octahedra defined in this way. In the above construction each of the possible choices for $B$ corresponds to a different octahedron. This set of five octahedra is also inscribed in a second regular icosahedron which is obtained by interchanging spokes with ring edges at the endpoints of each octahedral-edge connection.
