Abstract Post-asymptotic giant branch stars (post-AGB) in binary systems, with typical orbital periods between $\sim\!100$ to $\sim$ 1 000 days, result from a poorly understood interaction that terminates their precursory AGB phase. The majority of these binaries display a photospheric anomaly called ‘chemical depletion’, thought to arise from an interaction between the circumbinary disc and the post-AGB star, leading to the reaccretion of pure gas onto the star, devoid of refractory elements due to dust formation. In this paper, we focus on a subset of chemically peculiar binary post-AGBs in the Galaxy and the Magellanic Clouds (MCs). Our detailed stellar parameter and chemical abundance analysis utilising high-resolution optical spectra from VLT+UVES revealed that our targets span a $T_{\rm eff}$ of 4 900–7 250 K and [Fe/H] of −0.5 - −1.57 dex. Interestingly, these targets exhibit a carbon ([C/Fe] ranging from 0.5 - 1.0 dex, dependant on metallicity) and s-process enrichment ( $\textrm{[s/Fe]}\,\geq\!1$ dex) contrary to the commonly observed chemical depletion pattern. Using spectral energy distribution (SED) fitting and period–luminosity–colour (PLC) relation methods, we determine the luminosity of the targets (2 700–8 300 $\rm L_{\odot}$ ), which enables confirmation of their evolutionary phase and estimation of initial masses (as a function of metallicity) (1–2.5 $\textrm{M}_{\odot}$ ). In conjunction with predictions from dedicated ATON stellar evolutionary models, our results indicate a predominant intrinsic enrichment of carbon and s-process elements in our binary post-AGB targets. We qualitatively rule out extrinsic enrichment and inherited s-process enrichment from the host galaxy as plausible explanations for the observed overabundances. Our chemically peculiar subset of intrinsic carbon and s-process enriched binary post-AGBs also hints at potential variation in the efficiency of chemical depletion between stars with C-rich and O-rich circumbinary disc chemistries. However, critical observational studies of circumbinary disc chemistry, along with specific condensation temperature estimates in C-rich environments, are necessary to address gaps in our current understanding of disc-binary interactions inducing chemical depletion in binary post-AGB systems.