New fluorescent molecular sensors based on a calix[4]arene biscrown-6 ether as coordination site and BODIPY derivative as signaling unit were synthesized, and their photophysical properties were characterized. The complexation properties of these sensors with potassium and cesium cations were investigated using both steady-state and time-resolved fluorescence methods. The studies show that the sensitivity with cations depends upon the position of substituted coordination site on the BODIPY core. The complexation with cations does not have much effect on the absorption and emission wavelength when the coordination site (calix[4]arene biscrown-6 ether) is introduced at the meso position of the BODIPY core. In contrast, the same calix[4]arene biscrown-6 ether attached via a styryl linker to the a-position of BODIPY core leads to a sensitive sensor for alkali cations thanks to the better conjugation between the coordination site and the BODIPY core. The complexation of cations induces a hypsochromic shift of the absorption and emission maximums due to the diminution of donor character of the oxygen atoms in the coordination site. The stability constants of complexes with potassium and cesium ion were measured.