Dynamic combinatorial chemistry (DCC) has emerged as a versatile approach for generating and discovering materials with diverse applications. Utilizing acylhydrazone formation, we developed new dynamic combinatorial libraries (DCLs) of macrocycles and open-structured compounds with intriguing diversity. The DCL constituents were generated via condensation reactions using functionalized dihydrazides and aldehydes. Time-of-flight mass spectrometry (TOF-MS) was employed to analyze the library constituents, showcasing its great potential for characterizing DCLs generated by DCC. Our findings highlight the effectiveness of TOF-MS in verifying and validating complex macrocycles generated in solution, making it a valuable technique for discovering new materials through identification and validation of DCLs.