Pyridine and pyridine-derived skeletons represents an invaluable scaffolds in drug designing, and also an essential functionality for organic chemists [1]. Over the years, the chemistry of hybrid compounds containing imidazole/benzimidazole and pyridine moieties is developing, due to the fact that novel derivatives have important biological properties such as: anticancer, antimicrobial (antibacterial, antifungal, antitubercular), antimalarial, anti-inflammatory, antidepressant, analgesic, antihypertensive etc. [2-4]. Considering the above, our main objective was to synthesize and characterize novel hybrid quaternary salts with pyridine/benzimidazole skeleton adopting a general and straightforward strategy, involving three steps: I) N-acylation of 2-aminopyridine; II) N-alkylation of benzimidazole; II) quaternization reactions with halogenated derivatives with increased reactivity: p-substituted acetophenones. The structures of newly hybrid pyridine/benzimidazole quaternary salts were proved using NMR experiments (1H, 13C, 2D-correlations). The NMR apparatus (Bruker Advance III 500 spectrometer) is equipped with a 5 mm PABBO detection probe, operating at 500.1 MHz for 1H and 125 MHz for 13C.