I suppose that
Inactivate[Outer[Times, {x, y, z}, {x, y, z}], Times]
does not inactivate Times is because Times does not appear in Outer[Times, {x, y, z}, {x, y, z}]
as head of an expression. The documentation is somewhat unclear on this. Compare:
Inactivate[g[f], f]
Inactivate[f[g], f]