The synergistic effect of Ti, B, Si, and C on microstructure and mechanical properties of as-cast Al0.4Co0.9Cr1.2Fe0.9Ni1.2(Si, Ti, C, B)0.375 complex concentrated alloy (CCA) was studied. The as-cast alloy was prepared by vacuum induction melting in a ceramic crucible followed by a tilt casting to a graphite mould. The effect of alloying elements on the primary solidification phase, solidification path, and phase transformation temperatures is evaluated. The solidification of the alloy starts with the growth of columnar FCC(A1) (face-centred cubic crystal structure A1) dendrites and is finalised by the formation of lamellar FCC(A1) + (Ni,Co,Fe)16(Ti,Cr)6(Si,Al)7 eutectic in the interdendritic region. During solidification, Al, Ti, B, Si, and C segregate preferentially to liquid, which leads to the formation of BCC(B2) (ordered body-centred cubic crystal structure B2), BCC(A2) (body-centred cubic crystal structure A2), FCC(A1), (Ni,Co,Fe)16(Ti,Cr)6(Si,Al)7, Cr2B, and TiC phases in the interdendritic region. The highly anisotropic microstructure of tensile specimens prepared from the as-cast alloy consists of columnar FCC(A1) dendrites (89 vol%) oriented at an angle ranging from 75 to 90 degrees to the longitudinal axis of specimens and multiphase interdendritic region (11 vol%). The tensile deformation curves show only the strain hardening stage at test temperatures up to 700 °C. The strain hardening coefficient decreases from 0.20 to 0.17 by increasing the test temperature from 20° to 700°C. At temperatures ranging from 725° to 900°C, the tensile curves show the strain hardening stage, which is followed by the strain-softening stage up to a fracture. The strain softening stage results from dynamic recrystallisation of FCC(A1) dendrites and fracture of brittle high elastic modulus phases in the interdendritic region.