A ball sealer for hydrocarbon resource recovery, comprising: a generally spherical entire structure including at least two layers of a spherical core and a surface resin layer covering the spherical core, of which at least the surface resin layer comprises a polyglycolic acid resin; and having a diameter of at least about 25 mm (1 inch). The ball sealer is produced through a process comprising the steps of: disposing a spherical core by a support pin at a substantially central position within a mold cavity, injecting a surface resin comprising a polyglycolic acid resin into the cavity surrounding the spherical core, causing the support pin to retreat up to a wall surface of mold cavity in synchronism with a completion of the injection of the surface resin, and then hardening the surface resin. As a result, it is possible to produce a large-diameter ball sealer suitable for use in the hydraulic fracturing process (hydraulic fracturing) widely used for recovery of hydrocarbon resources by using a polyglycolic acid resin which is a biodegradable resin having good mechanical strengths and a good size designability at least as a surface-forming resin, through relatively simple steps and with good dimensional accuracy.