A multi-piece solid golf ball comprising a core, an envelope layer encasing the core, an intermediate layer encasing the envelope layer, and a cover which encases the intermediate layer and has formed on a surface thereof a plurality of dimples, wherein the core is made primarily of a rubber material and has a diameter of at least 31 mm, the envelope layer and intermediate layer are each made primarily of the same or different resin materials and the cover is made primarily of polyurethane; intermediate layer and cover have an optimized thickness relationship; the core, envelope layer, intermediate layer and cover have optimized hardness relationships; and the core surface and core center have a large hardness difference therebetween. The golf ball has excellent flight performance and controllability acceptable to professionals and other skilled golfers, while also having excellent durability to cracking upon repeated impact and excellent scuff resistance.