Detailed investigations of Ni substituted Fe 0.94 Ni 0.007 Te 0.66 Se 0.34 and unsubstituted Fe 0.99 Te 0.66 Se 0.34 crystals were performed at ambient and under hydrostatic pressure in order to understand complex relationship between the structure, magnetism, and superconductivity in iron selenides. The investigations aimed at determining structural and superconducting state properties and studying their evolution under pressure up to 11 kbar. Comparison of Fe 0.99 Te 0.66 Se 0.34 , a material with much less developed phase separation, with FeTe 0.5 Se 0.5 , a material exhibiting well pronounced nanoscale phase separation, was also performed. Under ambient pressure the weakening of superconducting state properties was observed in Fe 0.994 Ni 0.007 Te 0.66 Se 0.34 crystal, with disorder introduced by Ni substitution, as compared with those in Fe 0.99 Te 0.66 Se 0.34. For Fe 0.994 Ni 0.007 Te 0.66 Se 0.34 , the X-ray diffraction studies have revealed a degradation of crystal quality under applied elevated pressure. Superconducting state properties of single phase Fe 0.99 Te 0.66 Se 0.34 crystal, such as upper and lower critical