The host compound, H, featuring two fused tricyclic moieties, was successfully synthesised via a multistep procedure involving Grignard reaction, salt formation, and subsequent linkage with 1,4-diaminobutane. Its host capabilities were evaluated against several heterocyclic solvents. Selective formation of a 1:2 inclusion complex was observed exclusively with morpholine, while the remaining solvents exhibited no inclusion behaviour. Structural characterisation identified key supramolecular interactions responsible for stabilising the complex, and thermal analysis indicated a multi-step guest release accompanied by limited stability under ambient conditions. Furthermore, competition experiments confirmed H’s strong and enhanced selectivity for morpholine, particularly in binary mixtures with pyridine, yielding moderate selectivity coefficients.