In this work, we manifested a new approach in designing solid-state colorimetric sensors for the selective optical sensing of As³⁺. The sensor fabrication is modulated using, (i) a cubic mesopores of ordered silica monolith, and (ii) a bimodal macro-/meso-porous polymer monolith, as hosting templates that are immobilized with a tailor-made chromoionophoric probe (DFBEP). The surface morphology and structural dimensions of the monolith templates and the sensor materials are characterized using p-XRD, XPS, FE-SEM-EDAX, HR-TEM-SAED, FT-IR, TGA, and BET/BJH analysis. The sensing components such as pH, probe content, sensor dosage, kinetics, temperature, analyte concentration, linear response range, selectivity, and sensitivity are optimized to arrive at the best sensing conditions. The silica and polymer-based monolithic sensors show a linear spectral response in the concentration range of 2–300 and 2–200 ppb, with a detection limit of 0.87 and 0.75 ppb for As³⁺, respectively. The real-time ion-monitoring propensity of the sensors is tested with spiked synthetic and real water samples, with a recovery efficiency of ≥99.1% (RSD ≤1.57%). The sensors act as both naked-eye optical sensors and preconcentrators, with a response time of ≤2.5 min. The molecular and photophysical properties of the DFBEP-As³⁺ complex are studied by TD-DFT calculations, using the B3LYP/6–31G (d,p) method.