There is much scientific and commercial interest in plasma polymers to modify surface chemistry. To date, only neutral and positively charged species have been detected in the commonly applied acrylic acid plasma. Using time-averaged negative ion mass spectrometry, we demonstrate that large, negatively charged species exist in the plasma, contrary to previous studies that detected only neutral and positive species. We briefly outline how negative molecules may contribute to the deposition of plasma polymer in the acrylic acid system.