The DABCO-catalyzed [3 + 3] annulation between 3-nitro-2H-chromenes and benzyl 2,3-butadienoate has been developed as a route to 5H-chromeno[3,4-b]pyridine derivatives. Under optimal reaction conditions, 5H-chromeno[3,4-b]pyridines incorporating two allenoate units were obtained in moderate to good yields (30–76%). The same type of transformation could be carried out using butynoates as allene surrogates. Mechanistic studies by mass spectrometry allowed the identification of the key intermediates involved in the reaction mechanism. The reported synthetic methodology represents an entirely new approach for the synthesis of the 5H-chromeno[3,4-b]pyridine core structure based on allene chemistry.