The purpose of this work is to establish the influence of the nature of solid alginate gels (alginic acid, AAG; calcium alginate, CAG) and the conditions of methylene blue (MB) introduction to alginate matrices upon its release into aqueous media. MB is an active photosensitizer, which is used in the photodynamic therapy of tumors and purulent wounds. Solid alginate gels based on AAG and CAG were obtained by adding hydrochloric acid and calcium chloride to sodium alginate. The dye was introduced into the matrix either at the stage of gelation or by immersing the gel in an aqueous solution of the dye. It has been shown that the strength of the dye’s attachment to AAG is higher than that of CAG, which leads to a higher rate of MB release from CAG into aqueous media. It has also been shown that, when introduced at the stage of gel formation, MB is released into both the water and buffer solutions. When MB is introduced by gel immersion into an MB solution, the dye may be released only into salt solutions. An alginate gel with immobilized MB can be used as a solid photosensitizing system with the controlled release of the photoactive agent into the wound cavity for photodynamic treatment.