Trying to breathe in the vacuum of space would be rapidly fatal due to multiple factors, primarily the lack of atmospheric pressure and breathable oxygen. Your lungs would rupture, and your blood would boil.
Here's a breakdown of the consequences:
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Rapid Decompression and Lung Rupture: The sudden absence of external pressure would cause the air in your lungs to expand violently. Because you instinctively try to inhale, this would worsen the effect by expanding them even further. This expansion exceeds their structural capacity, leading to tearing and rupturing.
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Lack of Oxygen: Space is a vacuum, meaning there's virtually no atmosphere and, therefore, no oxygen. You would immediately be deprived of oxygen, leading to rapid loss of consciousness.
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Boiling of Bodily Fluids: The near-total vacuum of space dramatically lowers the boiling point of liquids. Your saliva, and eventually your blood, would begin to vaporize ("boil") within your body. This isn't the same as boiling at 212°F (100°C) on Earth; it's a phase change that occurs at much lower temperatures in a vacuum.
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Embolisms: As your blood boils, gas bubbles form within your circulatory system. These bubbles can block blood flow, leading to embolisms, causing immediate and severe damage to vital organs.
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Other Effects: Exposure to the radiation in space would also contribute to tissue damage. While the effects are not immediate, they would exacerbate the overall trauma.
In short, attempting to breathe in space would lead to a quick and gruesome death, resulting from lung rupture, oxygen deprivation, boiling bodily fluids, and embolisms.
