Herein, we developed a multisensor array utilizing multiple cholinesterase (ChE) and indoxyl acetate (IDA) sensors for the detection and differentiation of trichlorfon (Tri), profenofos (Pro), methomyl (Met), carbofuran (Car), phoxim (Pho), and pyridaphenthion (Pyr). The detection mechanism involves the inactivation of ChE by organophosphates (OPs) and carbamates (CMs), leading to a reduction in the production of indoxyl groups through IDA hydrolysis. We observed distinct and varied inhibition rates of the three enzymes in response to Tri, Pro, Met, Car, Pho, and Pyr. Linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA) plots illustrated the effectiveness of the system in accurately distinguishing both individual and mixed pesticides. Additionally, the platform showed the sensor array’s ability to identify pesticide mixtures and resist interference. Furthermore, the successful classification and determination of celery samples highlighted its practical applicability. This approach holds promise for developing a straightforward sensor array for detecting and discriminating pesticides in complex samples.