We synthesized spin crossover (SCO) complexes with inserted guest molecules; Fe[4-(3-pentyl)pyridine](2)[Au(CN)(2)](2)center dot guest. The insertion of guest molecules enhances the chemical pressure in the two-dimensional Hofmann-type frameworks and promotes the SCO behavior depending on the size of guest molecules of dichlorobenzene isomers. We found that the highest crossover temperature is achieved in the case of the shortest interlayer distance introducing the p-dichlorobenzene guest.