Disclosed herein is a sample collection apparatus which includes a pretreatment unit arranged in front of a sample collection section to remove moisture, a first Peltier trap positioned at the lower side of the pretreatment unit to perform cooling condensation and thermal desorption, a switching valve connected to the rear of the pretreatment unit to determine flow paths through first, second, third and fourth ports, a sample collection section arranged at the rear of the switching valve to collect samples, a second Peltier trap positioned at the lower side of the sample collection section to perform thermal desorption, a first air pump connected to the second port of the switching valve to intake air, a second air pump connected to the rear of the sample collection section to intake and exhaust air, and a sample analyzer connected to the fourth port of the switching valve to analyze the samples.