In a multi-piece solid golf ball having a core, an envelope layer, an intermediate layer, and a cover with a plurality of dimples thereon, the core is a two-layer core consisting of an inner core layer and an outer core layer each formed primarily of a base rubber, the envelope layer, the intermediate layer and the cover layer are each composed of at least one layer and formed primarily of a synthetic resin material, and the initial velocities and surface hardnesses of the core, the envelope layer-encased sphere and the intermediate layer-encased sphere are designed within specific ranges. This golf ball satisfies at a very high level the flight and control performances expected for use by professional golfers and skilled amateurs, has the ability to move forward on a straight path particularly on full shots, and also has an excellent scuff resistance.