Titan's ionosphere contains a rich positive ion population including organic molecules. Here, using CAPS electron spectrometer data from sixteen Titan encounters, we reveal the existence of negative ions. These ions, with densities up to ∼100 cm−3, are in mass groups of 10–30, 30–50, 50–80, 80–110, 110–200 and 200+ amu/charge. During one low encounter, negative ions with mass per charge as high as 10,000 amu/q are seen. Due to their unexpectedly high densities at ∼950 km altitude, these negative ions must play a key role in the ion chemistry and they may be important in the formation of organic-rich aerosols (tholins) eventually falling to the surface.