The structure of [Fe(Htrz)₂(trz)]BF₄ (1, Htrz =1,2,4-4-H-triazole, trz = 1,2,4-triazolate) at the low-spin (LS) and high-spin (HS) states and structural transitions between the two states were investigated by in situ high-resolution synchrotron X-ray powder diffraction (XRPD) combined with Raman spectroscopy using a modulation-enhanced technique. The crystal structures of the LS and HS states were determined. A 1D chain structure of 1 at both LS and HS states was proven, and the lattice expansion upon LS-HS transition was mainly caused by the elongation of the chain. The differences in the behavior of the spin transition observed by XRPD and Raman spectroscopy were explained by the local sensitivity of the two different techniques and also by the spatial propagation of spin crossover phase transition within the crystallite and the body of the grain. Moreover, we demonstrated that the two-dimensional correlation analyses facilitate (i) understanding the data obtained by combined techniques, (ii) clarifying correlation between the signals gained by the different probes, and (iii) extracting information on temporal evolution of transformation processes.