Plywood is fantastic. Look at the Mosquito! But more seriously, it was a designers dream from the day they got it "right" for tensile strength and glue/moisture issues.
MDF is kind of meh. It weighs a tonne, and it sucks paint up like a builder in the bar after work. But it has it's place. Damp.. nightmare.
(had work done on a wooden house in Qld, it made extensive use of GlueLam for structural support, Plywood for rigidity and wind shear load bearing, and MDF for routed patterns: walls and ceilings in Qld used (and still often are) made of (vertically joined, in the case of walls) Tongue-and-Groove or "vee-jay" and is very hard to get at old dimensions, and lumber from a "restoration station" (recycling centre) is very exy now. So for mixing new build with old build, MDF+router == same width pattern of VJ grooves.
If its structural and hidden (or not, if you like it's look) then manufactured wood is really great stuff.