The effect of complexant shape effect on the first hyperpolarizability beta(0) of alkalides Li(+)(NH(3))(4)M(-) (M=Li, Na, K) was explored. At the MP2/6-311++G level, Li(+)(NH(3))(4)M(-) (M=Li, Na, K) have considerable beta(0) values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li(+)(calix[4]pyrrole)M(-), a complexant shape effect in Li(+)(NH(3))(4)M(-) is detected. The beta(0) values of Li(+)(NH(3))(4)M(-) with the "smaller", inorganic, T(d)-symmetric (NH(3))(4) complexant are more than four times larger than those of Li(+)(calix[4]pyrrole)M(-) with the "larger", organic C(4v)-symmetric calix[4]pyrrole complexant. The ratios of the beta(0) values of Li(+)(NH(3))(4)M(-) and Li(+)(calix[4]pyrrole)M(-) are 6.57 (M=Li ), 6.55 (M=Na), and 5.17 (M=K). In the Li(+)(NH(3))(4)M(-) systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M(-) is -0.667 (M=Li )>-0.644 (M=Na)>-0.514 (M=K), while the order of the oscillator strengths in the crucial transition is 0.351 (M=Li )<0.360 (M=Na)<0.467 (M=K). This indicates that complexant shape effects are strong, and consequently the beta(0) values of Li(+)(NH(3))(4)M(-) are found to be beta(0)=70 295 (M=Li )<96 780 (M=Na)<185 805 a.u. (M=K). This work reveals that the use of a high-symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.