The octahedron has a much higher angular defect (https://en.wikipedia.org/wiki/Angular_defect) than the dodecahedron, and thus when it is projected onto the sphere the cells are warped a lot. So while their areas may be the same, the shapes vary.
Not sure I understand—healpix starts from the rhombic dodecahedron and then bisects the generalizations of the 12 squares each time. Where do octahedra come into play?
A5 cell boundaries are geodesics. One more difference that I thought of is that HEALPix is generally not aligned with the continents (makes sense as it is mostly used for astrophysics), whereas the hilbert curve used to index A5 is aligned with the continental land masses: https://a5geo.org/examples/globe
As a result, when A5 is used as a spatial index, it will generally not have jumps in the cell index values when querying nearby locations on land