解:设方程$x^2 - 21x + 21a - 1 = 0$的正整数根为$m,$则:
$m^2 - 21m + 21a - 1 = 0$
整理得:$21a = -m^2 + 21m + 1$
∴$a = \frac{-m^2 + 21m + 1}{21} = -\frac{m^2}{21} + m + \frac{1}{21}$
∵$a$为正整数,$m$为正整数
∴$-m^2 + 21m + 1$必须能被$21$整除,即$m^2 \equiv 1 \pmod{21}$
又
∵方程有实根,判别式$\Delta = (-21)^2 - 4(21a - 1) \geq 0$
$\begin{aligned}441 - 84a + 4 &\geq 0 \\445 - 84a &\geq 0 \\84a &\leq 445 \\a &\leq \frac{445}{84} \approx 5.3\end{aligned}$
∴$a$为正整数,$a \leq 5$
分别检验$m$为正整数且$m < 21$(由韦达定理,两根之和为$21,$正整数根$m$满足$1 \leq m \leq 20$):
当$m = 1$时:$a = \frac{-1 + 21 + 1}{21} = \frac{21}{21} = 1$(正整数,符合)
当$m = 20$时(另一根为$1$):$a = \frac{-400 + 420 + 1}{21} = \frac{21}{21} = 1$
当$m = 8$时:$m^2 = 64,$$64 \div 21 = 3\cdots1,$即$64 \equiv 1 \pmod{21}$
$a = \frac{-64 + 168 + 1}{21} = \frac{105}{21} = 5$(正整数,符合)
当$m = 13$时(另一根为$8$):$a = \frac{-169 + 273 + 1}{21} = \frac{105}{21} = 5$
综上,正整数$a$的值为$1$或$5$