An exhalate sampling apparatus, comprising an auxiliary device for exhalate collection upon a sampling adsorbent cartridge, which devices comprises: - a sampling chamber having an outlet port, the latter arranged in a intermediate position on said sampling chamber and apt to be put in communication with an environment which houses the sampling cartridge, said sampling chamber having also a further port for communication with the outside, arranged at said sampling chamber downstream of said outlet port with respect to a flow exhalate; - an inhalation chamber having a port for communication with the outside, the latter apt to allow inletting of outside air into the inhalation chamber; - first flow interdicting/enabling means of a passive-type, arranged between said sampling and inhalation chambers and apt to selectively put in communication these latter chambers; - second flow interdicting/enabling means of a passive-type, arranged at said port for communication with the outside of said inhalation chamber and apt to selectively allow an inletting of outside air into said inhalation chamber, - a single main body inside which said inhalation and sampling chambers are contained, said chambers being arranged in sequence with respect to the flow of exhalate, the inhalation chamber upstream of the sampling chamber, and substantially aligned along a longitudinal axis of the device, wherein said device further has an inlet port apt to be put in communication with a patient's mouth for receiving a flow of exhalate, which inlet port is arranged at said inhalation chamber and interposed between said port for communication with the outside and said first flow interdicting/enabling means, wherein said inlet port of said inhalation chamber and said outlet port of said sampling chamber are associated with a side skirt of said main body whereas said ports (22, 23) for communication with the outside are made at opposite longitudinal ends of the device, wherein the overall configuration is such that, during an expiratory act causing a flow of exhalate being inlet from said inlet port, said first means puts in communication said inhalation chamber with said sampling chamber and said second means interdicts the inletting of outside air into said inhalation chamber, and vice versa during an inspiratory act, and wherein said sampling apparatus comprises said adsorbent cartridge as sampling means which cartridge is arranged in the environment in communication with said outlet port, characterized in that said sampling apparatus futher comprises third flow interdicting/enabling means, of a passive-type, arranged at said further port for communication with the outside and apt to selectively set said sampling chamber in communication with the outside in the presence of an expiratory act, - a sampling chamber having an outlet port, the latter arranged in a intermediate position on said sampling chamber and apt to be put in communication with an environment which houses the sampling cartridge, said sampling chamber having also a further port for communication with the outside, arranged at said sampling chamber downstream of said outlet port with respect to a flow exhalate; - an inhalation chamber having a port for communication with the outside, the latter apt to allow inletting of outside air into the inhalation chamber; - first flow interdicting/enabling means of a passive-type, arranged between said sampling and inhalation chambers and apt to selectively put in communication these latter chambers; - second flow interdicting/enabling means of a passive-type, arranged at said port for communication with the outside of said inhalation chamber and apt to selectively allow an inletting of outside air into said inhalation chamber, - a single main body inside which said inhalation and sampling chambers are contained, said chambers being arranged in sequence with respect to the flow of exhalate, the inhalation chamber upstream of the sampling chamber, and substantially aligned along a longitudinal axis of the device,