In contrast to the wetting phenomenon of pure substance phase, we here concentrate on the wetting behavior of immiscible fluids with two components via numerical simulations. We investigate the energetic contribution, the wall energy and the surface excess energy, to the wetting behavior of liquid solutions varying with temperature. This investigation is in accordance with Cahn's wetting transition theory, where the surface composition plays a vital role. By analyzing the energetic contributions, we reveal two different physical mechanisms of complete wetting: (i) surface tension driven complete wetting, where the wetting microstructure is achieved via the outward spreading of the triple junction, and (ii) diffusion induced complete wetting, where the wetting film is achieved through a direct deposition of the solute on the substrate. The former one is consistent with the classic theory of Young's law, and the latter one is an alternative mechanism. To indicate the broad multiplicity of the microstructural arrangements, we take porous structures to exemplarily elucidate the formation of alternative perfect wetting structures. Differing from the wetting on a flat substrate, we show that the surface composition varying with temperature leads to a distinct wetting phenomenon in porous structures. The present findings provide an alternative interpretation for complete wetting and are expected to be exploited for designing more effectively and efficiently superhydrophilic structures.