Provided is a hydrophobic catalyst layer for a polymer electrolyte fuel cell to which hydrophobicity is imparted so that the dissipation property of produced water is improved and which simultaneously has an increased effective surface area and an increased utilization ratio of a catalyst, and a method of producing the same. The catalyst layer for a polymer electrolyte fuel cell includes a catalyst obtained by reducing a platinum oxide, a hydrophobic agent, and a proton conductive electrolyte, wherein the hydrophobic agent is mainly composed of alkylsiloxane. An Si compound containing a hydrophobic substituent is brought into contact with a platinum oxide to subject the Si compound to hydrolysis and a polymerization reaction by the catalytic action of the platinum oxide, and then it is reduced, thereby obtaining a hydrophobic catalyst layer carrying an alkylsiloxane polymer.