Rare earth doped mid-infrared (MIR) fluorescent sources have been widely investigated due to their various potential applications in the fields of communication, chemical detecting, medical surgery and so forth. However, with emission wavelength extended to MIR, multiphonon relaxation process that strongly quenched the MIR emission is one of the greatest challenges for such practical applications. In our design, we have described a controllable gas-aided annealing strategy to modulate the phase, crystal size, morphology and fluorescent performance of a material simultaneously. Uniform and monodispersed Er3+-doped La2O2S and La2O2SO4 nanocrystals with a similar lattice structure, crystallinity, diameter and morphology have been introduced to investigate the impact of multiphonon relaxation on luminescence performance. Detailed spectroscopic evolutions in the region of MIR, near-infrared (NIR), visible upconversion (UC) and their corresponding decay times provide insight investigation into the fluorescent mechanism caused by multiphonon relaxation. A possible energy transfer model has also been established. Our results present direct observation and mechanistic investigation of fluorescent evolution in multiphonon relaxation process, which is conductive to design MIR fluorescent materials in the future. To the best of our knowledge, it is the first investigation on MIR fluorescent performance of La2O2S nanocrystals, which may find various applications in many photoelectronic fields.