Objectives The COLCHIC database contains workplace exposure results of chemical samples collected by the French prevention network since 1987. We aimed to investigate potential associations between exposure levels and ancillary variables in COLCHIC across a broad range of chemical agents in order to provide insight into how to best interpret and exploit the information in this national database. Methods We selected personal and area measurements in COLCHIC and collected outside respiratory personal protective equipment (PPE), restricted to chemical agents that had at least 1000 samples available. We used Tobit models to estimate associations between exposure concentrations and sample year, sampling duration, PPE, workforce size, collective protective equipment, origin of request, and reason for request for each chemical agent for the period 1987–2019. Models for period 2002–2019 also included type of process (open/closed) and exposure frequency. We used separate models for each combination of agent, period, and personal or area samples. We then applied Bayesian meta-analytical methods to assess average effects and effect heterogeneity of exposure factors across agents. Results COLCHIC contained 720 282 exposure results (62% personal and 38% area samples) to 77 agents, including 346 766 results for the more recent period 2002–2019 (67% personal and 33% area samples). Sample year and duration, PPE, and process type had the strongest and most consistent associations with exposure levels across agents. Personal and area exposure levels decreased yearly (6% for the entire period and 9% since 2002), and 30-min samples were approximately twice as high as 240-min samples. Workers wearing PPE were exposed to levels 1.7 times higher on average than those without PPE for both area and personal samples. Personal exposure levels associated with enclosed or semi-enclosed processes were approximately 20–30% lower compared with open processes. The associations for the other exposure variables were weaker and more inconsistent between agents. Between-agent heterogeneity of estimated effects, based on 80% prediction intervals, was lowest for sampling duration, time trends, and the presence of PPE. Conclusions Sampling duration, time trends, and the presence of PPE are important factors to take into account when analyzing COLCHIC and had similar associations with exposure levels across agents. Other variables generally showed weaker associations or variable effects. These results will be used to adjust exposure estimates for the French working population from measurements stored in COLCHIC. [ABSTRACT FROM AUTHOR]