The biggest time sink I see is that you look up $netHash{$val} 100 times in each loop.

Untested code, via top-of-my-head refactoring: 

#!/usr/bin/perl
use strict;
use warnings; 

# Do you really need named hashes for later code?
my @capVal_hashes = (
    undef,
    \( my %capVal_1_Hash ), 
    \( my %capVal_2_Hash ),
    \( my %capVal_3_Hash ),
...
    \( my %capVal_99_Hash ),
    \( my %capVal_100_Hash ),
);

open IFH, '<', './chance.txt' or die;

my %netHash;
while (<IFH>) {
    my ( $key, $val ) = split;
    next if not $val > 1;

    my $hash_num    = ( $val <=   1.0 ) ? undef
                    : ( $val <    1.4 ) ?     1
                    : ( $val ==   1.4 ) ? undef # Intentional gaps?
                    : ( $val <    1.9 ) ?     2
                    : ( $val ==   1.9 ) ? undef # Intentional gaps?
    ...
    ...
                    : ( $val <   99.2 ) ?    98 # XXX Assumed
                    : ( $val ==  99.2 ) ? undef # Intentional gaps?
                    : ( $val <   99.8 ) ?    99
                    : ( $val <= 100.1 ) ? undef # Intentional gaps?
                    : ( $val <  100.9 ) ?   100
                    :                     undef
                    ;

    if ( defined $hash_num ) {
        $capVal_hashes[$hash_num]{$key} = $val;
    }
}
close IFH or warn;

foreach my $href ( @capVal_hashes ) {
    next if not defined $href;
    my @keys = keys %{ $href };
    my $random_key = @keys[ rand @keys ];
    my $random_val = $href->{$random_key};
    print "$random_key $random_val\n";
}

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In reply to Re: better way to printing random hash key and its value by Util
in thread better way to printing random hash key and its value by garbage777

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