Abstract We report the first detection on Titan of the small cyclic molecule cyclopropenylidene (c-C3H2) from high-sensitivity spectroscopic observations made with the Atacama Large Millimeter/submillimeter Array. Multiple lines of cyclopropenylidene were detected in two separate data sets: ∼251 GHz in 2016 (Band 6) and ∼352 GHz in 2017 (Band 7). Modeling of these emissions indicates abundances of 0.50 ± 0.14 ppb (2016) and 0.28 ± 0.08 (2017) for a 350 km step model, which may either signify a decrease in abundance, or a mean value of 0.33 ± 0.07 ppb. Inferred column abundances are (3–5) × 1012 cm−2 in 2016 and (1–2) × 1012 cm−2 in 2017, similar to photochemical model predictions. Previously the C3H ion has been measured in Titan’s ionosphere by Cassini’s Ion and Neutral Mass Spectrometer (INMS), but the neutral (unprotonated) species has not been detected until now, and aromatic versus aliphatic structure could not be determined by the INMS. Our work therefore represents the first unambiguous detection of cyclopropenylidene, the second known cyclic molecule in Titan’s atmosphere along with benzene (C6H6) and the first time this molecule has been detected in a planetary atmosphere. We also searched for the N-heterocycle molecules pyridine and pyrimidine finding nondetections in both cases, and determining 2σ upper limits of 1.15 ppb (c-C5H5N) and 0.85 ppb (c-C4H4N2) for uniform abundances above 300 km. These new results on cyclic molecules provide fresh constraints on photochemical pathways in Titan’s atmosphere, and will require new modeling and experimental work to fully understand the implications for complex molecule formation.