The invention discloses an atmosphere volatile organic compound condensation and concentration sampling device which comprises a low-temperature environmental cabinet and an atmosphere sampler, wherein a low-temperature cold trap device is arranged in the low-temperature environmental cabinet, and comprises a first-stage cold trap and a second-stage cold trap, the first-stage cold trap comprises a first condensation pipe and a first semiconductor chilling plate group, a first heating wire is wound on the first condensation pipe, the second-stage cold trap comprises a second condensation pipe and a second semiconductor chipping plate group, and a second heating wire is wound on the second condensation pipe. The invention also discloses an atmosphere volatile organic compound condensation and concentration sampling method. The atmosphere volatile organic compound condensation and concentration sampling device and method disclosed by the invention are capable of meeting the demand on online automatic monitoring of the content of a volatile organic compound, and can be used in on-site online automatic monitoring of the content of the atmosphere volatile organic compound.