Food safety is a burning global issue in this present era. The prevalence of harmful food additives and contaminants in everyday food is a significant cause for concern as they can adversely affect human health. More particularly, among the different food contaminants, the use of excessive pesticides in agricultural products is severely hazardous. So, the optical detection of residual pesticides is an effective strategy to counter the hazardous effect and ensure food safety. In this perspective, nanomaterials have played a leading role in defending the open threat against food safety instigated by the reckless use of pesticides. Now, nanomaterial-based optical detection of pesticides has reached full pace and needs an inclusive discussion. This Review covers the advancement of photoprocess-based optical detection of pesticides categorically using nanomaterials. Here, we have thoroughly dissected the photoprocesses (aggregation and aggregation-induced emission (AIE), charge transfer and intramolecular charge transfer (ICT), electron transfer and photoinduced electron transfer (PET), fluorescence resonance energy transfer (FRET), hydrogen bonding, and inner filter effect) and categorically demarcated their significant role in the optical detection of pesticides by luminescent nanomaterials over the last few years.