Two solvent-free two-dimensional (2D) coordination polymers, (2)∞[Fe(ptim)2] (1) and (2)∞[Fe(ptpy)2] (2) (Hptim = 2-(5-(4-(1H-imidazol-1-yl)phenyl)-4H-1,2,4-triazol-3-yl)pyridine; Hptpy = 2-(5-(4-(pyridin-3-yl)phenyl)-4H-1,2,4-triazol-3-yl)pyridine), have been successfully prepared by solvothermal reactions. Their iron atoms are bridged by the corresponding multidentate anionic ligands into dense neutral structures. The magnetic data reveal that complexes 1 and 2 are rare examples exhibiting reversible one-step high-temperature spin crossover behaviors with spin transition temperatures of 419 and 416 K, respectively. Moreover, these structures also display remarkable thermal stability up to 714 K (for 1) and 690 K (for 2), which are confirmed by thermogravimetric and variable-temperature powder X-ray diffraction analyses.