The adsorption of boron trichloride (BCl3) was explored onto pristine, S-doped, and Cr-doped graphyne through density functional theory computations. The interaction of BCl3 with pristine graphyne was weak and, thus, this sheet cannot be used as a sensor. Although S-doping strengthens the interaction, the S-doped sheet cannot still be used as a sensor. However, the reactivity and sensitivity of the sheet are significantly increased toward BCl3 by replacing the C atom of graphyne with the transition metal Cr. The HOMO-LUMO gap of Cr-doped graphyne reduces from 2.18 to 1.38 eV following the adsorption of BCl3, which significantly increases the electrical conductivity. Thus, the great change in the conductivity can be converted into an electronic signal, indicating that Cr-doped graphyne may be a promising sensor for BCl3. Also, its work function is considerably decreased by the adsorption process, indicating that it can also work as a work function-type sensor for BCl3 detection.