We demonstrate direct frequency-comb (FC) spectroscopy of the dipole-forbidden 4s 2 S 1=2 -3d 2 D 5=2 transition in trapped 40 Ca þ ions using an unamplified FC laser. The excitation is detected with nearly 100% efficiency using a shelving scheme in combination with single-ion imaging. The method demonstrated here has the potential to reach hertz-level accuracy, if a hertz-level linewidth FC is used in combination with confinement in the Lamb-Dicke regime. © 2010 Optical Society of America OCIS codes: 300.6520, 120.3940, 140.7090.Optical frequency combs (FCs) provide a direct link between optical and microwave frequencies [1,2]. This link enables carrying the accuracy of a microwave frequency standard to the optical domain, or transferring the extreme accuracy achieved in optical spectroscopy (currently reaching below the 10 −17 level [3]) to any other part of the optical spectrum and to the microwave domain. In addition, the development of broadband titaniumdoped sapphire FC lasers with a wavelength span of hundreds of nanometers [4,5] makes high-accuracy frequency calibration possible over a very wide wavelength range. These FCs can be employed to calibrate an additional laser that is used for excitation, but it is also possible to directly use the light of the comb modes to perform the metrology [6][7][8][9]. This technique of direct FC spectroscopy (DFCS) is advantageous in that the full comb spectrum is available for excitation, without the need for an additional probe laser.Trapped laser-cooled ions provide an ideal system for DFCS, as they allow for long interaction times. Furthermore, different ionic species can be trapped simultaneously and be sympathetically cooled and detected by the laser-cooled ions [10,11]. The application of DFCS to trapped ions [9] thus facilitates spectroscopy on various ionic transitions in a single measurement setup. To our knowledge, the possibility of DFCS of trapped ions has been demonstrated only for strong resonance lines. The range of applicability of this method would be greatly extended if also weak and narrow transitions could be detected. For example, such a "clock" transition could be used as an in situ frequency reference for the calibration of other transitions in ions or as a probe for external fields in the ion trap. The concept of DFCS on narrow transitions has been investigated for cold neutral calcium atoms on a transition with a linewidth of 374 Hz, using the amplified modes of an FC [12]. In this Letter, we show that DFCS can be performed on significantly weaker transitions, using an ion trap and even without amplification of the FC laser. This is demonstrated on a laser-cooled crystal of calcium ions, in which the dipoleforbidden 4s 2 S 1=2 -3d 2 D 5=2 transition at 729 nm (natural linewidth 0:14 Hz) is induced with DFCS. On this transition, one can potentially reach hertz-level accuracy, as was shown previously by Chwalla et al. using cw laser excitation [13].In our experiment, calcium ions are produced by twophoton excitation involving a frequency-double...