The widespread adoption by agronomists and researchers of handheld leaf chlorophyll meters stimulates enquiries on instrumental calibration issues, given the necessity, for some applications, of inferring actual chlorophyll concentrations from the readings provided. This is especially required for recently developed and more innovative devices such as the Dualex (Force-A, France), which unlike the more common SPAD-502 (Minolta, Japan) has not undergone extensive (published) calibration tests. Additionally, devices for spectral reflectance measurements are also becoming increasingly available. In the present paper, the calibration of SPAD on maize (Zea mays L.) and of Dualex on winter wheat (Triticum aestivum L.), durum wheat (Triticum durum Desf.), horse bean (Vicia faba L.) and maize, was compared to spectral reflectance indices and full spectral information (400–2500 nm) acquired by a spectroradiometer (ASD FieldSpec) equipped with a contact probe and leaf clip. Full spectral data were exploited using partial least squares regression (PLSR). The measurements were performed in the field at Maccarese (Central Italy) in 2012, gathering a specific experimental dataset. The calibration models obtained on experimental data for SPAD (on maize) and Dualex (on four crops) showed intermediate or high estimation accuracy with root-mean-square error (RMSE) values ranging between 7 and 11 μg/cm2 depending on the species. These results were slightly better than those achieved using spectral reflectance indices, which were inferior though to those provided by PLSR using full spectral resolution. A synthetic database, generated by the physically based PROSPECT model, simulating hemispherical leaf reflectance and transmittance, was used to compare the performances of the reflectance indices and the chlorophyll meters for a wider range of leaf properties. The results confirmed the substantial equivalence of reflectance-based and transmittance-based (i.e. simulated SPAD and Dualex) indices and the advantage of exploiting the full spectral information, e.g. through PLSR, if available.