This paper describes the fabrication of polyelectrolyte multilayer film which combines preassembly of poly(allylamine hydrochloride) (PAH) and 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p '',p '''-tetrasulfonic acid tetrasodium hydrate (TPPS) in aqueous solution with the layer-by-layer (LbL) assembly of the PAH-TPPS complex and cross-linkable polyelectrolyte, PAASH(60), which is a poly(acrylic acid) with 60% of its carboxylic acid grafted of thiol groups. During preassembly, TPPS was incorporated into PAH chains. After oxidative cross-linking to form disulfide bonds in between the layers, the multilayer with preassembly of the PAH-TPPS complex allowed for release and loading of TPPS in a reproducible way. The release of TPPS from the loaded film was a pH-controlled process. To compare with the conventional multilayer, the reloading capacity was greatly enhanced, which was related to the charge binding sites that formed by release of TPPS from the multilayer. Moreover, the release of TPPS could also be achieved by breaking off the cross-linking through reduction of disulfide bonds, and the release rates could be controlled by the reductive efficiency of the reductants in the media. In this way, the release of TPPS is pH/reductant dually controllable, thereby facilitating a new route to multistimuli controllable materials.